DE69532651T2 - METAL FILM COMPOSITE BODY, LINKING LAYER AND BINDING AGENT - Google Patents

Description

TECHNICAL TERRITORY

This invention relates to one covered with a metal film Body, an adhesive layer and an adhesive, and particularly strikes an adhesive and an adhesive layer with excellent toughness without lowering the Heat resistance, electrical insulating property and chemical stability and various covered with a metal film body with excellent adhesive property between a carrier and an applied metal.

Lately are for printed Circuits and printed circuit boards with mounted LSI have a high compression and reliability through a fine pattern corresponding to the miniaturization and the High speed performance of electronic equipment with the progress of the electronics industry required.

As a method of forming the Conductor on the printed wiring board has been around lately an additive method has become known, in which an adhesive a surface of a carrier applied to form an adhesive layer and then roughened the surface and subjected to chemical plating.

According to this procedure, the Conductor formed by chemical plating after the formation of a resist, so that it has the preference that a conductor wiring with high Density and pattern accuracy at a low cost compared to an etched one Foil process can be produced, in which the pattern formation by etching takes place (subtractive procedure).

In the additive process so far a method has been known in which a fine bump on the conductor-forming surface side the adhesive layer by chemical etching as a means of improvement the adhesive property between the conductor and the adhesive layer (hereinafter referred to as "peel strength").

At the recently manufactured printed circuit of the additive type, which the formation of wiring with high density and pattern accuracy is required required less adhesion, formed by roughening the surface the adhesive layer, to create the fine pattern of the resist train exactly. If the adhesion becomes low, the fracture area is small, so that a problem is caused that the peel strength considerably is lowered.

On the other hand, the last one Time metallic parts through plastic parts by improving of engineering plastics in the fields of automotive and Transportation equipment, in the fields of electrical and electronic parts and machines, in the field of household items, in the field of construction technology and been replaced in the medical field.

There are e.g. B. the housing and a fixed ring of a camera using polycarbonate, called a bearing made of polyacetal and the like. Furthermore is a gearbox or the like, made from super high molecular weight polyethylene Service.

In these plastic parts it can however, the surface of the part may need to be covered with a metal film in terms of design, corrosion resistance, abrasion resistance and the like to cover.

As a means of covering the plastic surface with A method has previously been proposed for the metal film in which formed an adhesive layer on the surface of the plastic carrier and the surface the adhesive layer roughened and covered with the metal film becomes.

JP-B-58-44709 describes e.g. B. a Process in which an adhesive for chemical plating consisting of acrylonitrile butadiene rubber and epoxy resin, on one surface an insulating support applied and then the epoxy resin part of the surface of the Dissolved adhesive layer and is removed to the surface roughening and then chemical plating is performed around a metal film coating to build.

Furthermore, JP-A-61-276875 describes a method wherein an adhesive for chemical plating obtained by Disperse fine powder of heat-resistant resin in a heat-resistant resin matrix the carrier applied and then its surface by treating the fine Heat-resistant resin powder roughened with an oxidizing agent and then chemical plating is carried out.

In the technical plastic (carrier resin), which is covered with the metal film through the adhesive layer, however Problems observed that cracks due to the difference in the coefficient of thermal expansion between the carrier resin and the adhesive layer in the heat cycle and that cracks in the adhesive layer itself be formed at the time of tension formation.

Chemical plating and adhesive printed circuits are described in EP-A-0 625 537.

In order to solve these problems, there is a method for increasing the strength of the coating metal or the heat-resistant resin matrix forming the adhesive. However, according to the inventors' attempts, it is It has been confirmed that peeling of the chemically plated film constituting the coating metal is caused by breaking the heat-resistant resin matrix in the conventional art using copper as the coating metal and the thermosetting resin or the photosensitive resin as the adhesive-forming heat-resistant resin matrix. That is, it has been observed that the strength of the heat-resistant resin matrix constituting the adhesive is lacking as a reason for lowering the bond strength. Furthermore, it has been confirmed that the reason for cracking in the heat cycle or stress formation is also the low strength of the heat-resistant resin matrix.

To the various above Problems in conventional Technique to solve It is therefore an object of the present invention to use the adhesive forming heat-resistant resin matrix to reinforce without the heat resistance, to lower the electrical insulation property and the chemical stability.

It is another object of the invention an adhesive layer with excellent adhesive properties to the coating metal provide.

It is the other object of the invention to provide a technique that is capable of stably different Metal film coatings for printed Circuits with improved peel strength even in high density wiring with high pattern accuracy and other industrial parts.

DESCRIPTION THE INVENTION

The inventors have various studies in terms of to improve the strength of the heat-resistant resin matrix forming the adhesive carried out, to accomplish the above tasks. As a result it is established that a mixed resin of an uncured, thermosetting resin containing a Resin in which some of its functional groups are photosensitive Group is substituted, and / or an uncured, photosensitive Resin and a thermoplastic resin as the adhesive-forming heat-resistant resin matrix is used, and a resin composite obtained by curing this Resin is used as an adhesive layer, whereby a coated with a metal film Body, like a carrier for printed Wiring or the like, provided with excellent adhesive strength to the conductor metal even if the one formed by a roughening treatment Sticking depth is small, and the invention has been completed.

This means,

(1) the adhesive according to the invention is an adhesive obtained by the method as defined in any one of claims 1-3 is. One by dissolving Removable or removable particulate substance is in an uncured, heat resistant resin matrix dispersed in which the heat-resistant resin matrix one in terms of tolerance adapted resin matrix, consisting of a thermoplastic Resin and at least one or two resins selected from an uncured thermosetting Resin containing a resin in which some of its functional Groups is substituted by a photosensitive group (herein hereinafter simply as an unhardened thermosetting Resin) and an unhardened photosensitive resin. This resin mixture is preferred in one acceptable Condition by dissolving in a solvent or in incompatible Status.

If the resin mixture is in the compatible Condition is a quasi-homogeneous, compatible structure, a co-continuous Phase structure or spherical Domain structure, how later mentioned by Adjust the phase separation speed and the hardening speed when hardening the mixture can be obtained.

If the resin mixture in the incompatible Condition is spherical Domain structure through hardening the mixture as it is.

As a particulate substance that can be removed by dissolution is it desirable to use at least one particle selected from inorganic particles, Metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble Resin particles.

As removable by decomposition, particulate Substance it is desirable a suspension-polymerized, low-crosslinking amino resin or the like to use.

In the invention, the term "removal by Resolution "that the resolution and Decomposition of the particulate Substance by chemical action using a roughening solution such as an acid, an alkali, an oxidizing agent, water, an organic solvent or similar are evoked during the expression "distance by decomposition "means that the decomposition of the particulate substance by heating, loading with pressure or atmospheric setting, like humidity adjustment or the like, without using the Aufrauungslösung is caused.

Further, the "resin mixture of the thermoplastic resin and at least one or two resins selected from thermosetting resins and photosensitive resins" used in the invention means (1) a resin mixture of thermosetting resin and thermoplastic resin, (2) a resin mixture mixture of photosensitive resin and thermoplastic resin or (3) a resin mixture of thermosetting resin, photosensitive resin and thermoplastic resin.

Another glue is a glue obtained by dispersing a resin solution that is not with the matrix compatible is in an uncured, heat resistant resin matrix before curing and removal by dissolution after curing, characterized in that the heat-resistant resin matrix has a respect of tolerance set resin mixture of a thermoplastic resin and at least is one or two resins selected from uncured, thermosetting Resins and uncured, photosensitive Resins.

The other glue is a glue obtained by mixing an uncured, heat-resistant resin matrix with a Resin solution which is compatible with the resin matrix is before curing and removal by dissolution by phase separation after curing, characterized in that that the heat-resistant matrix one in terms of tolerance set resin mixture of a thermoplastic resin and at least one or two resins selected from uncured, thermosetting Resins and uncured, photosensitive resins.

If such a resin mixture in the acceptable Condition is present, a quasi-homogeneous, compatible structure, a co-continuous Phase structure or spherical Domain structure, as mentioned later, by Setting the phase separation speed and the curing speed when curing the mixture can be obtained.

If the resin mixture is incompatible Condition is present, a spherical domain structure can be obtained by curing the Mixture as it is.

(2) An adhesive layer with a roughened surface is on a carrier by dispersing a dissolvable or by Decomposition removable, granular Substance in a cured, heat resistant resin matrix formed, which is a resin composite consisting of a thermoplastic Resin and at least one or two resins selected from a thermosetting Resin containing a resin in which some of its functional Groups is substituted by a photosensitive group (herein hereinafter simply as an unhardened thermosetting Resin) and an uncured, photosensitive Resin. This resin composite is preferred for the formation of a quasi-homogeneous, compatible structure, a co-continuous phase structure or a spherical domain structure.

As a particulate substance that can be removed by dissolution is it desirable to use at least one particle selected from inorganic particles, Metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble Resin particles.

As removable by decomposition particulate Substance it is desirable a suspension-polymerized, low-crosslinking amino resin or the like to use.

The other adhesive layer with one roughened surface is on a carrier by dispersing a dissolvable resin in one cured heat resistant resin matrix formed, which is a resin composite consisting of a thermoplastic Resin and at least one or two resins selected from a thermosetting Resin and a photosensitive resin in the form of countries for education a sea-land structure. This resin composite is preferred for formation a quasi-homogeneous, compatible Structure, a co-continuous phase structure or a spherical domain structure.

As a resin removable by dissolution it is desirable a resin that with the uncured, heat resistant resin matrix before curing not compatible and a "sea-land structure" with this resin matrix forms inhomogeneous state after curing, and a resin, the one with the uncured, heat resistant resin matrix before curing compatible is to use what is a phase separation from this resin matrix while of curing caused and a "sea-land structure" with the resin matrix inhomogeneous state after curing.

The phase separation during the curing comprises (1) phase separation caused by the curing of the Matrix resin, (2) a phase separation caused by the curing of both the matrix and the dissolvable resin, and (3) phase separation caused by heat (temperature) supplied in the curing and fixation of the phase by curing.

In addition, the term "sea-land structure" means that in the invention is used that the heat-resistant resin matrix forms a sea, and that parts of high concentration of the removable by dissolution Resin in the sea in an inhomogeneous state of concentration in Form of countries, in which the border between sea and land is unclear. These countries can differ from each other be separated by the sea, or some countries can be continuous.

In such an adhesive layer the roughened surface formed by dissolving or decompose by dissolution Removable or removable particulate substance or by dissolution removable resin with land structure from the surface the adhesive layer.

Can be used as a carrier of circuit boards Be used that are provided with a circuit and industrial are applicable in various forms, such as fibrous, rod-shaped, spherical and the like.

(3) The body covered with a metal film comprises a support, an adhesive layer with a roughened surface on its side to be coated with a metal and a metal film arranged on the roughened surface of the adhesive layer, characterized in that the adhesive layer is formed by dispersing a particulate substance which can be removed by dissolution or can be removed by decomposition in a hardened, heat-resistant resin matrix which is a resin composite consisting of a thermoplastic resin and at least one or two resins selected from a thermosetting resin containing a resin in which part of its functional groups are substituted by a photosensitive group (hereinafter simply referred to as an uncured thermosetting resin) and an uncured photosensitive resin. This resin composite is preferred for the formation of a quasi-homogeneous, compatible structure, a co-continuous phase structure or a spherical domain structure.

As a particulate substance that can be removed by dissolution is it desirable to use at least one particle selected from inorganic particles, Metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble Resin particles. As a particulate substance that can be removed by decomposition is it desirable a sus pension polymerized, low crosslinking amino resin or the like to use.

The other covered with a metal film body includes a carrier, an adhesive layer with a roughened surface on it with a metal to be overdrawn Side and one arranged on the roughened surface of the adhesive layer Metal film, characterized in that the adhesive layer by dispersing one in a cured, heat resistant resin matrix by dissolution removable resin is formed, which is a resin composite made of a thermoplastic resin and at least one or two Resins, selected from a thermosetting Resin and a photosensitive resin in the form of countries Formation of a sea-land structure. This resin composite is preferred for the formation of a quasi-homogeneous, acceptable Structure, a co-continuous phase structure or a spherical domain structure.

As a resin removable by dissolution it is desirable a resin that with the uncured, heat resistant resin matrix before curing and the formation of a "sea-land structure" with this resin matrix in the inhomogeneous state after curing is not compatible, and a resin containing the uncured, heat-resistant resin matrix before curing compatible is to use what is a phase separation from this resin matrix while of curing causes and with the resin matrix in inhomogeneous state after the Harden forms a "sea-land structure".

Can be used as a carrier of printed circuit boards with a conductor circuit and various forms that can be used industrially Can be used such as fibrous, rod-shaped, spherical and the like.

In the one covered with a metal film body becomes the plate as a support is used and an applied metal is etched if necessary, or a metal is printed in the form of a pattern to form a Circuit applied.

Such is a printed circuit a printed circuit in which an adhesive layer formed by dispersing the one by dissolution Removable or removable particulate substance in the cured, heat resistant matrix z. B. on the carrier formed and the roughened surface on the surface of the Adhesive layer is formed, which is to be provided with the conductor, and the conductor circuit is also arranged on the roughened surface , characterized in that the heat-resistant resin matrix is a resin composite is composed of a thermoplastic resin and at least one or two resins selected made of thermosetting Resin and photosensitive resin. The resin composite is preferred to form a quasi-homogeneous, compatible structure, a co-continuous Phase structure or spherical Domain structure.

The other printed circuit includes a carrier, an adhesive layer formed thereon by dispersing countries by dissolution removable resin in a sea of a cured, heat-resistant resin matrix from a resin composite from a thermoplastic resin and at least one or two resins made of thermoplastic resin and photosensitive resin for formation a sea-land structure and provided with a ladder-forming, roughened surface and a conductor circuit arranged on the roughened surface, characterized in that the heat-resistant resin matrix is a resin composite made of a thermoplastic resin and a thermosetting resin and / or photosensitive resin. The resin composite is preferred for formation a quasi-homogeneous, compatible Structure, a co-continuous phase structure or a spherical domain structure.

SHORT DESCRIPTION THE DRAWINGS

1 Fig. 10 is a flow chart explaining the stages of manufacturing an embodiment of the printed circuit according to the invention.

2 is a graph showing results of dynamic viscoelasticity measured on the resin composite with a quasi-homogeneous, compatible structure according to the invention.

3 is a TEM photograph of a crystal structure, which has a quasi-homogeneous, compatible structure shows the resin composite according to the invention.

4 Fig. 5 is an SEM photograph of a crystal structure showing a spherical domain structure of the resin composite according to the invention.

5 Fig. 4 is a flow chart showing the manufacturing steps of another embodiment of the printed circuit according to the invention.

6 Fig. 5 is an SEM photograph of a crystal structure showing a co-continuous phase structure of the resin composite according to the invention.

7 is a graph showing results of dynamic viscoelasticity measured on the resin composite with a co-continuous phase structure according to the invention.

8th is an SEM photograph of a crystal structure in section of an adhesive layer after drying and before curing.

9 is an SEM photograph of a crystal structure in section of the adhesive layer after hardening.

10 Fig. 10 is a phase diagram showing the relationship between the drying temperature of a CNA 25 / PES / TMPTA mixture and the state of the resin composite after curing.

11 Fig. 10 is a phase diagram showing the relationship between the drying temperature of a CNA 25 / PES mixture and the state of the resin composite after curing.

12 Fig. 10 is a phase diagram showing the relationship between the drying temperature of an epoxy / PES mixture and the state of the resin composite after drying.

13 Fig. 3 is an SEM photograph of a crystal structure in section of the adhesive layer, showing a state of decomposable granules (low polymerized melamine resin) before decomposition.

14 Fig. 5 is an SEM photograph of a crystal structure in section of the adhesive layer, showing a state of decomposable granules (low polymerized melamine resin) after decomposition.

In these figures the reference number is 1 a carrier, the reference number 2 an adhesive layer, the reference number 3 a resist, the reference numerals 4 . 6 . 8th and 10 are conductors, and the reference number 5 is a through opening.

BEST EMBODIMENT THE INVENTION

(1) An essential feature of the Adhesive according to the invention lies in the point that the adhesive matrix is a mixture of "an uncured, thermosetting Resin including of a resin in which some of its functional groups a photosensitive group is substituted (hereinafter simply as an uncured, thermosetting Resin) and / or an uncured, photosensitive Resin "and" a thermoplastic Resin ". In the Adhesive according to the invention is it particularly desirable that the resin mixture of the thermoplastic resin and at least one or two resins from the uncured, thermosetting Resin and the uncured photosensitive resin, homogeneously mixed in the compatible state. In this way the resin matrix of the adhesive can be reinforced without the heat resistance, the electrical insulation properties and chemical stability are reduced become.

The reason why the resin mix of the tolerable State as a heat resistant resin matrix of the Adhesive used is based on the fact that the resin structure of the resin composite, consisting of the thermoplastic resin and at least one or two resins selected from the cured thermosetting Resin and the photosensitive resin, easily due to the curing conditions can be regulated.

As a method of homogeneous mixing and dispersing at least one or two resins selected from the uncured, thermosetting Resin and the uncured, photosensitive resin, compatible with the thermoplastic resin in ver There is a process of dissolving these resins in one state Solvent, a method of melting the thermoplastic resin Heat and mixing with the thermosetting Resin or the photosensitive resin and the like. In particular the process of dissolving the resins in the solvent preferably used because the resins are tolerated at a low level Temperature with good processability can be resolved.

Dimethylformamide can be used as the solvent (DMF), normal methyl pyrrolidone (NMP), methylene chloride, diethylene glycol dimethyl ether (DMDG) and the like to be named.

In the adhesive according to the invention, it is desirable that the mixing ratio of at least one or two resins selected from the uncured, thermosetting Resin and the uncured, photosensitive resin, to the thermoplastic resin in the heat-resistant resin matrix 15 to 50 wt .-% as the content of the thermoplastic resin.

If the content of the thermoplastic Resin is less than 15 wt .-%, the toughness of the adhesive layer can not be improved while if it exceeds 50% by weight it is difficult to apply the adhesive and a smooth and even layer of adhesive to build.

The viscosity of the adhesive according to the invention is desirably 0.5 to 10 Pa · s, measured at 25 ° C. If the viscosity Exceeds 10 Pa · s, the job property is lowered and it cannot smooth adhesive surface be obtained while if it is less than 0.5 Pa · s, deposition becomes the one by dissolution Removable or removable particulate substance caused, and a sufficiently roughened surface can not be obtained, and the adherence to the applied Metal is lowered.

(2) An essential feature of the Adhesive layer according to the invention lies in a point that a resin composite made of a thermoplastic Resin and at least one or two resins selected from a thermosetting Resin, including a resin in which some of its functional groups are replaced by a photosensitive group (hereinafter simple) as uncured, thermosetting Resin) and a photosensitive resin as the resin matrix the adhesive layer is used. In this way, the adhesive layer with an excellent adhesive property to the applied metal be provided in a stable manner.

The reason why the resin composite from the thermoplastic resin and at least one or two resins, selected from the thermosetting Resin and the photosensitive resin, as the heat-resistant resin matrix of the adhesive layer is based on the fact that the resin composite Properties that the thermosetting Resin or photosensitive resin are inherent, and toughness, inherent in the thermoplastic resin, and therefore the entire resin matrix can be reinforced without the heat resistance, the elasticity, to lower the electrical insulation property and the chemical stability.

The surface of the adhesive layer according to the invention is roughened, but the roughened surface is covered by so-called trap-like Octopus recessed parts used to dissolve or decompose the resolution Removable or removable particulate substance capable or formed by land-dispersed, dissolvable resin. Therefore, these recess parts form adhesion points for metal coatings that are deposited by chemical plating or the like, and the resin matrix forming the recess part has great toughness and hardly causes the resin to break, so the adhesive strength (Peel strength) can be maintained high without the metal coating of the roughened surface the adhesive layer peels off.

Furthermore, the heat resistant resin matrix excellent toughness, so that it hardly breaks, even if the adhesive layer itself is one Deformation is subjected, and can even be used when the carrier is subjected to deformation or tension.

In the adhesive layer according to the invention, the resin composite is desired to form a quasi-homogeneous, compatible structure, a co-continuous phase structure or a spherical domain structure. Here
(a) the term "quasi-homogeneous, compatible structure" means a state that in the resin composite of the thermosetting resin or the photosensitive resin and the thermoplastic resin there is a so-called phase diagram of the LCST type (low critical solution temperature), the particle size being constituent resin particles is not more than 0.1 μm as measured by a transmission electron microscope, and the peak value of the glass transition temperature of the resin as measured by the dynamic viscoelasticity is one. Such a state is close to an ideal mixing state of the resin and is a new concept discovered by the inventors. The conditions for measuring the dynamic viscoelasticity are an oscillation frequency of 6.28 rad / s and a temperature rise rate of 5 ° C / min.

That means the quasi-homogeneous, compatible structure is a more homogeneous structure, which has an effect for the introduction of Has properties that are higher are as those which are the thermoplastic resin such as polyether sulfone (PES) or similar, inherent are the properties which the thermosetting resin such as epoxy resin or are inherent in the photosensitive resin such as acrylic resin, be maintained and it is very strong in the interaction between the thermosetting Resin or photosensitive resin and the thermoplastic resin.

The structure of this resin composite is confirmed by the fact that the broken surface condition of the resin composite cannot be changed and is homogeneous, even after etching with a solvent, which dissolves the thermoplastic resin.

In the resin composite, which is the quasi-homogeneous, compatible Structure forms are the breaking strength and the tensile strength higher than those of each resin that forms the resin composite.

The effect due to the structure of this resin composite is particularly striking if the content of the thermoplastic resin (for example PES) in the resin composite is 15 to 50% by weight as a solids content. If the content of the thermoplastic resin is less than 15% by weight, the molecule of the thermoplastic resin entangled in a network of the resin component is smaller, and the toughness effect is not sufficiently developed, while if it exceeds 50% by weight, the interaction becomes kung between the thermoplastic resin and the thermosetting resin or photosensitive resin little due to the decrease the number of networking points.

The quasi-homogeneous, compatible structure is formed by dissolving the uncured, thermosetting Resin or uncured, photosensitive resin and thermoplastic resin in one Solvent, if necessary, and mix evenly of the components and subsequent acceleration the curing speed and / or delay the phase separation rate so that a particle size of not more than 0.1 μm results, measured by means of a transmission electron microscope.

Specifically, there is the first procedure a method in which curing at a curing rate, which exceeds a point forming a quasi-homogeneous phase, determined by at least one factor selected from the curing temperature of the thermosetting Resin, the type of curing agent and the presence or absence of photosensitivity in the In case of using the thermosetting Resin, or at a curing rate, which exceeds a point forming a quasi-homogeneous phase, carried out is determined by light-curing Factors of the photosensitive resin, such as initiator, sensitizer, photosensitive monomer, exposure conditions and the like, in the case of using the photosensitive resin. The one in here expression used "a quasi-homogeneous phase forming point "means a lower limit of the curing rate, which is capable of maintaining a quasi-homogeneous, compatible structure, that the particle size of the Composite resin particle is not larger than 0.1 μm than one value measured by TEM observation.

There is a second procedure Process in which curing is performed at a phase separation rate which does not exceed the point forming a quasi-homogeneous phase, determined by at least one functional group number per one molecule and molecular weight in the uncured thermosetting resin or uncured, photosensitive resin. In this case it means a quasi-homogeneous Phase forming point an upper limit of the phase separation speed, which is capable of maintaining a quasi-homogeneous, compatible structure, that the particle size of the composite forming resin particle is not larger than 0.1 μm as a value measured by TEM observation.

The third procedure is one Process in which the curing at a curing speed, which exceeds the point forming the quasi-homogeneous phase, and is carried out in a phase separation phase which is the quasi-homogeneous Phase forming point does not exceed. This means that the factors affecting the curing speed and determine the phase separation speed, influence each other.

Now the relationship between the above factors, the curing speed and the Determine phase separation speed, described. First is the factor affecting the rate of curing determined as follows if the other factors are constant:

• (1) The curing speed becomes faster when the curing temperature of the thermosetting resin is high. If the thermosetting resin so hardened is that the lower limit of the curing temperature that will provide the curing speed, which exceeds the point forming the quasi-homogeneous phase the structure of the resulting resin composite is therefore one quasi-homogeneous, compatible Structure.
• (2) The curing rate gets faster when the gel time is short. If the thermosetting resin using a curing agent hardened will, so the upper limit of gel time required for the deployment the gel time required for the quasi-homogeneous phase exceeds not exceeded the structure of the resulting resin composite is therefore one quasi-homogeneous, compatible Structure.
• (3) The curing speed becomes faster when there is sensitivity to light. If the Photosensitivity of the resin in combination with other factors, which is the quasi-homogeneous, tolerable Form structure, is present, is therefore the resulting resin composite a quasi-homogeneous, tolerable Structure.

As a method of imparting sensitivity to light there is a procedure of introduction a photosensitive group in the thermosetting resin or the thermoplastic Resin and a method of mixing a photosensitive Monomers, in which a photo initiator or a photosensitizer can be added if required.

In addition, instead of thermosetting Resin is a photosensitive resin such as acrylic resin or the like, be used. In this case, it is necessary that the photosensitive Resin at a curing rate hardened should be, which exceeds the point forming the quasi-homogeneous phase, determined by light-curing Factors such as initiator, sensitizer, photosensitive monomer, Exposure conditions and the like.

However, when the photosensitivity of the thermosetting resin is given, or when the light sensitive monomer is used to improve the resolution in development, the compatibility of the uncured thermosetting resin or the uncured photosensitive resin with the thermosetting resin is lowered, causing phase separation at a relatively low temperature (see. 10 - 12 ). Therefore, when the photosensitivity of the thermosetting resin is given, or when the photosensitive monomer is used, the adhesive is dried at a low temperature (30-60 ° C) and, if necessary, immediately cured under reduced pressure and by exposure to light and then hardened by heat (80–200 ° C), whereby the quasi-homogeneous, compatible structure can be obtained.

If you consider the above circumstances, if the variable factor in the bond formation between the thermosetting Resin or the photosensitive resin and the thermoplastic Resin is one, is the value of the factor corresponding to that quasi-homogeneous phase forming point a point. If the factors are two or more, the value of the factor is equal to that the quasi-homogeneous phase forming point as different combinations consider. This means, the combination for the curing speed can be selected like this be the particle size of the Composite resin of not more than 0.1 μm as a value is measured through TEM observation.

• (1) Es ist schwierig, die Phasentrennung zu erhalten, wenn die Anzahl der funktionellen Gruppen pro einem Molekül des unausgehärteten, wärmehärtbaren Harzes oder des unausgehärteten, lichtempfindlichen Harzes groß wird (die Phasentrennungsgeschwindigkeit wird langsam). Wenn die Aushärtung durchgeführt wird durch Verwendung des unausgehärteten, wärmehärtbaren Harzes oder des unausgehärteten, lichtempfindlichen Harzes mit der Anzahl der funktionellen Gruppen pro einem Molekül, welche die untere Grenze der Anzahl der funktionellen Gruppen übersteigt, die für die Bereitstellung der Phasentrennungsgeschwindigkeit erforderlich ist, welche den die quasi-homogene Phase bildenden Punkt nicht übersteigt, hat der erhaltene Harzverbund eine quasi-homogene, verträgliche Struktur.
• (2) Es ist schwierig, die Phasentrennung zu erhalten, wenn das Molekulargewicht des unausgehärteten, wärmehärtbaren Harzes oder des unausgehärteten, lichtempfindlichen Harzes groß wird (die Phasentrennungsgeschwindigkeit wird langsam). Wenn das Aushärten durchgeführt wird durch Verwendung des unausgehärteten, wärmehärtbaren Harzes oder des unausgehärteten, lichtempfindlichen Harzes mit einem Molekulargewicht, welches die untere Grenze des Molekulargewichts übersteigt, die für die Bereitstellung der Phasentrennungsgeschwindigkeit erforderlich ist, welche den die quasi-homogene Phase bildenden Punkt nicht übersteigt, hat daher der resultierende Harzverbund eine quasi-homogene, verträgliche Struktur. Wenn man die vorstehenden Umstände berücksichtigt, wenn der variable Faktor bei der Verbundbildung zwischen dem wärmehärtbaren Harz oder dem lichtempfindlichen Harz und dem thermoplastischen Harz eins ist, ist der Wert des Faktors entsprechend zu dem die quasi-homogene Phase bildenden Punkt ein Punkt. Wenn die Faktoren zwei sind, ist der Wert des Faktors entsprechend zu dem die quasi-homogene Phase bildenden Punkt durch verschiedene Kombinationen zu berücksichtigen. Das heißt, die Kombination für die Phasentrennungsgeschwindigkeit kann so ausgewählt werden, dass sie der Teilchengröße des den Verbund bildenden Harzes von nicht mehr als 0,1 μm genügt, gemessen durch TEM-Beobachtung.

Next, if the other factors are constant, the factor that determines the phase separation rate is as follows:

• (1) It is difficult to obtain phase separation when the number of functional groups per one molecule of the uncured thermosetting resin or the uncured photosensitive resin becomes large (the phase separation speed becomes slow). When curing is carried out by using the uncured thermosetting resin or the uncured photosensitive resin having the number of functional groups per one molecule exceeding the lower limit of the number of functional groups required to provide the phase separation rate required by the does not exceed the quasi-homogeneous phase-forming point, the resin composite obtained has a quasi-homogeneous, compatible structure.
• (2) It is difficult to obtain phase separation when the molecular weight of the uncured thermosetting resin or the uncured photosensitive resin becomes large (the phase separation speed becomes slow). When curing is carried out by using the uncured thermosetting resin or the uncured photosensitive resin having a molecular weight exceeding the lower limit of the molecular weight required to provide the phase separation rate which does not exceed the point forming the quasi-homogeneous phase , the resulting resin composite therefore has a quasi-homogeneous, compatible structure. Taking the above circumstances into account, when the variable factor in the bond formation between the thermosetting resin or the photosensitive resin and the thermoplastic resin is one, the value of the factor corresponding to the point forming the quasi-homogeneous phase is a point. If the factors are two, the value of the factor corresponding to the point forming the quasi-homogeneous phase must be taken into account by various combinations. That is, the phase separation rate combination can be selected to satisfy the particle size of the composite resin of not more than 0.1 μm as measured by TEM observation.

In the resin composite with one quasi-homogeneous, compatible Structure, epoxy resin can be used as a thermosetting resin. In this case it is desirable that the epoxy resin is an epoxy equivalent from about 100-1000 Has. The reason for this is that it is difficult to find an epoxy resin with an epoxy equivalent of less than 100 while producing the epoxy equivalent Exceeds 1000, it’s difficult to mix it with the thermoplastic resin, like PES or the like, to mix, and also the phase separation is due to heating for curing the lowering of the Tg point caused by the quasi-homogeneous, compatible Structure hardly arises. The molecular weight of the epoxy resin is desirably 200-10000. If the molecular weight of the epoxy resin is less than 200, the not get sufficient response speed, and itself when it's cured the hardened Product hard and brittle, while if the molecular weight of the epoxy resin exceeds 10,000, the compatibility becomes lowered with the thermoplastic resin.

PES can also be used as a thermoplastic Resin can be used. In this case the molecular weight is from PES desirably 3,000 to 100,000. If the molecular weight of PES is less than 3000, the Effect of toughness improvement through the quasi-homogeneous, tolerable Structure not preserved during if it exceeds 100,000, can the tolerable Condition with the thermosetting Resin or the photosensitive resin cannot be formed.

As mentioned above, the resin composite having the quasi-homogeneous, compatible structure has the inherent properties of the thermosetting resin such as epoxy resin or the like, or the inherent properties of the photosensitive resin such as acrylic resin or the like, and can have properties ten higher than those inherent in the thermoplastic resin such as PES or the like. That is, PES-modified epoxy resin or PES-modified acrylic resin has high strength compared to that of the PES resin alone and has a solidifying effect on the epoxy resin or the photosensitive resin which has never been achieved with the conventional technique.

(b) The term "co-continuous phase structure" means a composite structure, in which spherical Particles containing a high proportion of thermosetting resin such as epoxy resin or similar, contained, continuously present in the matrix, which is high Portion of thermoplastic resin such as PES or the like contains (published by Takashi INOUE et al., POLYMER, 30, p. 662 (1989)).

Such a structure of the resin composite is confirmed from the fact that if the broken surface the resin composite with a solvent dissolving the thermoplastic resin etched the matrix part with a high content of thermoplastic Resin dissolved being, with only the connected spherical particles of the epoxy resin or similar to be watched.

The resin composite, which is the co-continuous Phase structure has great toughness compared to that wärmehärtbaeen Resin, such as epoxy resin alone, because the thermoplastic resin with a excellent toughness is in the form of a continuous phase.

(c) The term "spherical domain structure" means a state that spherical domains of thermosetting Resin or photosensitive resin separated and uniform in the matrix of the thermoplastic resin are dispersed.

Such a structure of the resin composite is confirmed by the fact that if the broken area the resin composite with a solvent dissolving the thermoplastic resin etched the matrix part with a high content of thermoplastic Resin dissolved , causing only the separated and uniformly dispersed spherical particles of the epoxy resin can be observed.

The Harzverbund, which is one spherical domain structure is tough than the thermosetting resin alone because the spherical Particles of the thermosetting Resin in a "sea" of thermoplastic Resin are dispersed.

The effect of co-continuous Phase structure or spherical domain structure of the resin composite is particularly striking if the content of the thermoplastic resin (e.g. PES) in the resin composite 15-50% by weight as the solids content. When the content of the thermoplastic resin is less than 15 % By weight is the molecule of the thermoplastic resin entangled in a network of the resin component is, smaller, and the toughness effect is not sufficiently developed, while if it exceeds 50% by weight, the interaction between the thermoplastic resin and the thermosetting or photosensitive resin small due to the decrease in the number from networking agencies.

In the resin composite, it is desirable that the average particle size of the spherical particles, which is the co-continuous phase structure or the spherical domain structure form, more than 0.1 μm, however not more than 5 μm is. When the average particle size of the spherical particle not more than 0.1 μm is, it is difficult to understand the co-continuous phase structure or the spherical Domain structure too form while if it exceeds 5 μm, can improve toughness can not be achieved, and the photosensitivity and heat resistance are getting worse.

In addition, the above called co-continuous phase structure or the spherical domain structure formed by (1) rules of the substitution ratio of functional Groups and photosensitive groups that are used to heat-harden the thermosetting Contribute resin, or (2) by adjusting the type and molecular weight the photosensitive resin to mix the uncured, thermosetting or photosensitive resin with the thermoplastic resin in a tolerable or incompatible State and then the setting of the drying or curing conditions in such a way that there is an average particle size of the constituted spherical particles of more than 0.1 μm, however not more than 5 μm results.

Likewise, at least one or two resins selected from thermosetting Resins and photosensitive resins, used as the resin matrix, and the thermoplastic resin can form a joined or independent spherical domain Resin can be used.

As mentioned above, is it is desirable that the adhesive layer according to the invention a quasi-homogeneous, tolerable Structure, a co-continuous phase structure or a spherical domain structure forms. Among them, the formation of the quasi-homogeneous, tolerable Structure a high resin strength compared to the formation of the co-continuous phase structure or the spherical domain structure, so that it is preferred to use the quasi-homogeneous, compatible structure as a resin matrix for the Form adhesive layer.

Furthermore, it is desirable that the thickness of the adhesive layer according to the invention Is 10-200 μm. If the thickness is less than 10 μm, the peel strength decreases, while if it exceeds 200 μm, the solvent hardly removed in the glue and it is difficult to dry and curing perform.

(3) The body covered with a metal film according to the invention is one covered with a metal film drawn body comprising a carrier, a roughened adhesive layer formed on the surface of the carrier, and a metal film disposed on the roughened surface of the adhesive layer, and is at a point that a heat-resistant resin matrix of the adhesive layer is a resin composite of a thermoplastic resin and at least one or two resins selected from thermoplastic resin including a resin in which part of its functional groups are substituted by a photosensitive group (hereinafter simply referred to as "thermosetting resin") and photosensitive resins.

In this case, it is desirable that the resin composite has a quasi-homogeneous, compatible structure, a co-continuous Phase structure or spherical domain structure forms.

The surface of the adhesive layer in the covered with a metal film body according to the invention is roughened, but the roughened surface is so called trap-like octopus recessed parts that are used to dissolve or Decompose by dissolution Removable or removable particulate substance or the land-dispersed, dissolvable resin. Therefore, these recess parts form traps for the chemical plating or the like deposited Metal coating, and the resin matrix, which the recess part forms, has a high toughness and hardly causes the resin to break, so the adhesive strength (Peel strength) to a great extent can be maintained without the metal coating of the roughened surface the adhesive layer peels off.

In the one covered with a metal film body according to the invention becomes a cardboard as a carrier used, and a plating metal is etched in the form of a pattern or applied thereon in the form of a pattern, whereby a printed Circuit can be made. In addition, such printed circuit can be multi-layered.

In this case, it is desirable that the roughened surface Rmax = 1-20 μm. If Rmax is less than 1 μm, will be the desired one Adhesion did not get while if it exceeds 20 μm, It is difficult to use a fine pattern printed circuit board To produce a sample spacing of no more than 100 μm.

According to such a printed Circuit can the heat-resistant resin matrix forming the adhesive without degradation heat resistance, elasticity, chemical stability and the electrical insulation property can be enhanced, and thus in a stable manner the printed circuit with an excellent peel strength can be provided even with high density of wiring and pattern accuracy.

In the glue, the adhesive layer and the one covered with a metal film body according to the invention, as mentioned above can phenolic resins, amino resins such as melamine resin, urea resin or the like, Epoxy resin, epoxy modified polyimide resin, unsaturated Polyester resin, polyimide resin, urethane resin, diallyl phthalate resin, etc. as a thermosetting Resin in the heat-resistant resin matrix can be used because these resins have excellent thermal and electrical Have properties. In the thermosetting Resin can be a part of the functional groups that contribute to heat curing locally substituted by a photosensitive group. So is z. B. a 5-70% acrylated epoxy resin preferred.

As a thermoplastic resin, which in the heat-resistant matrix use can be made of polyethersulfone (PES), polysulfone (PSF), phenoxy resin, polyetherimide (PEI), polystyrene, polyethylene, Polyarylate, polyamidoimide, polyphenylene sulfide, polyether ketone, polyoxybenzoate, Polyvinyl chloride, polyvinyl acetate, polyacetate, polycarbonate and the like. These thermoplastic resins have high heat resistance and toughness and can with the thermosetting Resin by using a solvent compatible be made.

Among them are the epoxy resin or the polyethersulfone (PES) as a thermosetting Resin or thermoplastic resin preferred.

The reason for this is that the quasi-homogeneous, compatible Structure, the co-continuous phase structure or the spherical domain structure in a simple manner by mixing and dispersing the epoxy resin and PES as a component of the resin matrix in a solvent, such as methylene chloride, dimethylformamide or the like can be formed.

It has also been confirmed that when used a mixed system of epoxy resin and PES modified the PES Epoxy resin which forms quasi-homogeneous, compatible structure reinforce the matrix, and the tensile strength and the elongation are not less than 1.5 times better compared to the corresponding properties of the epoxy resin alone. About that in addition, the inventors have confirmed that even if the depth of adhesion is the same, the peel strength the chemically plated layer in the printed circuit below Use of the adhesive or adhesive layer according to the invention is higher due to the above reinforcement the resin matrix than in the case of using the epoxy resin alone Resin matrix.

In the invention, resins, which are provided with photosensitive groups, or resins which mixed with a resin or monomer with photosensitivity as the above-mentioned thermosetting resin and / or thermoplastic Resin can be used.

In the case of resin composites with the quasi-homogeneous, compatible Structure when the photosensitive group the thermosetting Resin or the like is given, the photosensitive resin can be cured and brought in composite form by exposure to light for a short time without phase separation, and therefore the quasi-homogeneous, compatible Structure can be easily formed. In the case of resin composites with the co-continuous phase structure or the spherical domain structure it is easy to control the particle shape (particle size or the like) of the structure.

In the invention, a photosensitive Resin instead of incorporating photosensitive groups in it thermosetting resin be used. As the photosensitive resin, use can be made of those with one or more unsaturated double bonds, such as the acryloyl group, the methacryloyl group, the allyl group, the Vinyl group and the like, in their molecule, which preferably comprises epoxy acrylate, polyester acrylate, polyether acrylate, Silicone acrylate, polybutadiene acrylate, polystyrylethyl methacrylate, Vinyl / acrylic oligomer (obtained by copolymerizing branched Acid, Acid anhydride, monomer with hydroxyl groups and glycidyl groups with vinyl or acrylic polymer and then Reaction with acrylic monomer), polyethylene / thiol (copolymer of olefin and mercaptan) and the like.

As a photo initiator, as a light-curing Factor of the photosensitive resin is important can use be made of at least one intramolecularly cleavable by light Compound such as benzoisobutyl ether, benzyldimethyl ketal, diethoxyacetophenone, Acyloxime esters, chlorinated acetophenone, hydroxyacetophenone and the like, and of intramolecular hydrogen-releasing compounds, such as Benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, Isobutylthioxane and the like.

As a photo-initiating aid can be made use of at least one of triethanolamine, Michler's ketone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethyl benzoate, Ethyl 4-dimethylaminoethyl benzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, Isoamyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, polymerizable tertiary Amine and the like.

Michlers are as photosensitizers Ketone, Irgaqua 651, isopropylthioxanthone and the like are preferred. Some The above photo initiators act as photosensitizers.

In addition, the composition ratio of the photoinitiator and the photosensitizer based on 100 parts by weight of the photosensitive resin is preferably as follows. Benzophenone / Michler's ketone = 5 parts by weight / 0.5 parts by weight; Irgaqua 184 / Irgaqua 651 = 5 parts by weight / 0.5 parts by weight; Irgaqua 907 / isopropylthioxanthone = 5 parts by weight / 0.5 parts by weight

As a photosensitive monomer or photosensitive oligomer which form the photosensitive resin, are preferred epoxy acrylate, epoxy methacrylate, urethane acrylate, Polyester acrylate, polystyryl methacrylate and the like are used.

As a curing agent for the resin matrix according to the invention, if the epoxy resin as a thermosetting Resin is used, hardeners can be used of the imidazole type, diamine, polyamine, polyamide, anhydrous organic Acid, Vinyl phenol and the like. On the other hand, if thermosetting resins other than epoxy resin are used, can known curing agents be used.

Next, the one that is removable by resolution or particulate substance which can be removed by decomposition and which is present in the Invention is used and the dissolvable resin that in a land-like, dispersed state in the sea of the heat-resistant resin matrix is used, described in detail.

(1) As removable by dissolution, particulate Substance can be made of "hardened, heat-resistant resin powder, which can be used in acid or soluble in an oxidizing agent is "or" at least one by dissolution removable, particulate Substance, selected from inorganic particles, metal particles, elastomer particles, resin particles, the soluble in alkali and resin particles in solvent soluble are".

(a) As for "hardened heat-resistant resin powder, soluble in acid or oxidizing agent", the reason for using such a heat-resistant resin powder is based on the fact that after the hardening treatment, the heat-resistant resin powder in a diluted solvent containing the thermosetting resin, the photosensitive resin and the thermoplastic resin dissolves, becomes insoluble, and thus when the viscosity of the resin solution is lowered by the diluting solvent, the cured heat-resistant resin powder is uniformly dispersed in the resin solution. Further, when it is intended to obtain the resin composite having the quasi-homogeneous, compatible structure, the solvent for mixing the thermosetting resin or the photosensitive resin with the thermoplastic resin is used in a compatible state, but even in this case, it is cured tied, heat-resistant resin powder is not dissolved in the solvent, and thus clear traps can be formed.

Furthermore, the reason which is why the powder is in acid or oxidizing agent soluble is based on the fact that the oxidizing agent has a strong decomposing power has and can form a clear detention place in a short time and one excellent productivity has, and also the adhesive layer with formed by the oxidizing agent Detention centers are among the ordinary Conditions of use hardly dissolves or dismantles.

On the other hand, the acid is in the Neutralization treatment is not necessary as it is the oxidizer shows, and economical, and also the treatment of waste liquid is easy compared to the oxidizing agent or the like and needed simple equipment and has excellent security.

Can be used as heat-resistant resin powder made of epoxy resin, amino resin (melamine resin, urea resin, Guanamine resin), polyester resin, bismaleimide triazine resin, etc.

(b) what "at least one removable by dissolution, particulate Substance, selected from inorganic particles, metal particles, elastomer particles, in Alkali soluble Resin particles and solvent-soluble resin particles "refers to as inorganic Particles can be made use of oxides such as silica Aluminum oxide, zirconium oxide, zinc oxide, magnesium oxide, cordierite, titanium earth and similar, Carbides such as silicon carbide, boron carbide and the like, nitrides such as aluminum nitride, Boron nitride, silicon nitride and the like, Carbonates, such as calcium carbonate, sodium carbonate and the like, Sulfates such as barium sulfate and the like, Talc, etc.

The reason for using such inorganic particles is based on the fact that they have an effect the reduction in the coefficient of thermal expansion the heat-resistant resin matrix (resin composite) have and the consistency across from the heat cycle can improve. In particular, the thermal conductivity The adhesive layer can be improved if the inorganic particles with a high thermal conductivity, such as silicon carbide, aluminum nitride or the like can be used.

Can be used as metal particles are made of aluminum, nickel, magnesium, copper, zinc, iron etc.

The reason for using such Metal particle is based on the fact that electromagnetic properties the adhesive layer itself can be given.

Use as an elastomer particle made of rubbery resins such as polybutadiene rubber, Butadiene-styrene rubber, butadiene-acrylonitrile rubber, polychloroprene rubber, Polyisoprene rubber, acrylic rubber, synthetic multi-sulfur rubber, Urethane rubber, fluororubber, silicone rubber, ABS resin and the like, thermoplastic elastomers, such as polyester elastomer, thermoplastic Polystyrene-polybutadiene-polystyrene elastomer (SBS elastomer), thermoplastic, polyolefinic elastomer (TPO), thermoplastic polyvinylchloride elastomer and similar.

The reason for using such Elastomer particles are based on the fact that they are not heat-resistant particles and are relatively cheap and effectively reduce costs.

As the alkali-soluble resin particle, use can be made are made from cellulose resins such as cellulose nitrate, cellulose acetate, Cellulose acetate butyrate, cellulose propionate, ethyl cellulose, etc.

The reason for using such soluble in alkali Resin particles are based on the fact that they are in the neutralization treatment unnecessary are, as shown in the oxidizing agent, and economical and the treatment of waste liquid are easy to compare with the oxidizing agent or the like is simple equipment need and have excellent security.

As in solvent (organic solvent) soluble Resin particles can be made use of thermoplastic Resin powder such as styrene resin, vinyl chloride resin, vinyl acetate resin and the like.

The reason for using the in solvent soluble Resin particle is based on the fact that the surface of the Adhesive layer without using an oxidizing agent, such as chromic acid or the like, can be roughened, and therefore it is not necessary that waste liquid undergo a neutralization treatment and the production costs can be reduced.

In addition, the inorganic Particles and the metal particles insoluble in a dilute solvent, which is the thermosetting resin, dissolves the photosensitive resin and the thermoplastic resin, and thus the inorganic particles or metal particles become uniform in the Dispersed resin solution, if the viscosity the resin solution through the dilution solvent is reduced. If it is still intended, the resin composite with the quasi-homogeneous, compatible To get structure, the solvent for mixing the thermosetting Resin or photosensitive resin with the thermoplastic Resin in a tolerable way State used, but even in this case the inorganic ones Particles or metal particles are not dissolved in the solvent, and thus can clear detention areas are formed.

(2) As the decomposable particulate substance, use of emulsion-polymerized amino resins (melamine resin, urea resin, guanamine resin) with a low degree of crosslinking can be used be made.

The reason for using such a particulate substance removable by decomposition is based on the fact that the emulsion-polymerized low melamine resin Degree of crosslinking under high humidity, high temperature and high Pressure is decomposed, forming formalin and melamine monomers become. Therefore, it is not necessary for the roughening treatment the surface of the adhesive layer in a special roughening solution to immerse, and thus the manufacturing equipment becomes easy and is beneficial.

(3) The removable by dissolution Resin, which is in a land-like, dispersed state in the sea of heat-resistant resin matrix is used

As such resin, use can be made become from a resin that is not compatible with the uncured, heat-resistant resin matrix before curing and with this resin matrix a "sea-land structure" in an inhomogeneous state after curing and a resin that is compatible with the uncured, heat-resistant resin matrix before curing, which causes phase separation from this resin matrix during curing and with the resin matrix a "sea-land structure" in an inhomogeneous state after curing forms.

The former resin is a silicone resin with terminal Epoxy groups.

The latter resin are rubbery Resins such as butadiene, ABS resin and the like, and thermoplastic Resins such as polyester elastomer and the like as mentioned above. The rubbery resin dissolves z. B. in a phase solvent for the uncured, heat resistant resin matrix on, but is incompatible with the uncured, heat resistant resin matrix itself, so that the inhomogeneous state of concentration (sea-land structure) by creating zones (countries) with a high rubbery resin concentration in the uncured, heat resistant resin matrix (Sea) occurs.

Such a resin solution that forms a "sea-land structure" is difficult in terms of the size of the "country" and the Maintaining quality is difficult. In terms of at this point, mass production is difficult compared to previously hardened Resins used to regulate particle size by sieving and simple Regulation of quality and the inorganic and metal particles which the hardening treatment require, empowered are.

Furthermore, the curing conditions be adjusted to the uncured, heat resistant resin matrix in the quasi-homogeneous, tolerable To transfer structure. Self regarding this point, if the uncured resin solution is present, as above should be called the curing condition this resin solution set become what is disadvantageous.

However, the resin solution that forms a "sea-land structure" contains no solid components, such as the resin cured above, inorganic particles, metal particles and the like, so that it is in one point that the kneading time is shorter and that the glue solution is easy can be manufactured. Furthermore, the viscosity becomes easy degraded so that the smoothness and the job quality of the film applied are.

As the granular substance, various shapes such as a spherical shape, a hollow shape, a powdered bar shape and the like can be used in the invention. In particular, it is desirable to choose from ( 1 ) Particles with an average particle size of not more than 10 μm, ( 2 ) Aggregate particles with an average particle size of 2-10 μm by aggregating powder with an average particle size of not more than 2 μm, ( 3 ) a mixture of powder with an average particle size of 2-10 μm and powder with an average particle size of 2 μm and ( 4 ) artificial particles obtained by adhering at least one powder with an average particle size of not more than 2 μm and inorganic powder with an average particle size of not more than 2 μm to the surfaces of powder with an average particle size of 2-10 μm. That is, when the average particle size exceeds 10 μm, the adhesive effect becomes deep, and so-called fine patterns of not more than 100 μm cannot be formed while using the aggregate particle ( 2 ) the mixture ( 3 ) or the artificial particles ( 4 ) is desired due to the formation of complicated adhesion spots and improvement of the peel strength.

It is desirable that the surface of the particulate Substance with silica sol or the like is coated to prevent aggregation.

It is desirable that the amount of particulate matter 5-100 as a weight ratio, based on 100 parts of resin solids content in the heat-resistant resin matrix is. If the weight ratio is less than 5, no liability can be formed while it exceeds 100, kneading becomes difficult, and the heat-resistant resin matrix becomes relative reduced, which lowers the strength of the adhesive layer.

In the invention, epoxy resin is used as a thermosetting resin component which uses the heat resistant resin matrix in a roughening solution such as acid or oxidizing agents hardly soluble is while Epoxy resin powder as a heat-resistant resin powder that can be used in the roughening solution, such as acid or oxidizing agent, soluble is. This is related to the solubility against the oxidizing agent described.

The properties of epoxy resin can be found in differ widely by the type of prepolymer (polymer with relative low molecular weight with a molecular weight of about 300-10000), the type of curing agent and the networking density are regulated.

The difference in properties can be seen in the solubility compared to the oxidizing agent. The resin can be adjusted to any solubility by 1 ) the skeletal structure of the monomer and the curing agent, ( 2 ) the network structure and ( 3 ) the crosslinking density can be selected in a suitable manner. The points ( 1 ) and ( 2 ) are main factors, while the point ( 3 ) is used in a supportive manner.

As for the skeletal structure of the monomer , aliphatic epoxy has the highest solubility during which Glycidylamine type and the Glycidylether type the lowest solubility to have.

As for the network structure, so has the hydroxy ether structure obtained by the reaction of Epoxy and amine, a particularly high solubility, while the Ether structure obtained by reacting epoxy in the presence of imidazole as a curing catalyst, a particularly low solubility receives.

The crosslink density decreased themselves when the epoxy equivalent gets bigger and thus solubility high. Furthermore, the lowering of the solubility is achieved by the Epoxy monomer is converted into multifunctionality. Decreased in the phenol novolak type the solubility when the repeating unit n of the monomer gradually changes from 0 on 1, 2 and the like increases.

Based on the difference of solubility across from therefore, the oxidizing agent uses the "oxidizing agent-soluble epoxy resin" which is the heat-resistant resin powder matters, e.g. B. (A) "epoxy resin, that using aliphatic epoxy as the epoxy prepolymer and aliphatic amine curing agent as a hardening agent moderately networked is and the epoxy equivalent to about 265 ".

In contrast, as "epoxy resin, which in Oxidizing agent hardly soluble (including insoluble) "which is one thermosetting resin component the heat-resistant resin matrix is, (B) "epoxy resin with an epoxy equivalent of about 170 by using bisphenol A type epoxy resin as an epoxy prepolymer and aromatic diamine curing agent as curing agent "and (C)" epoxy resin with a epoxy equivalent of about 136 by using phenol novolak type epoxy resin as the epoxy prepolymer and Imidazole curing agent as a hardening agent, "which is a lower solubility Has.

Furthermore, the epoxy resin (B) as "in oxidizer soluble Epoxy resin "used and in this case the epoxy resin (C) is called "in oxidizing agent hardly soluble Epoxy resin "used.

As seen from the above examples, the feature that it is soluble or hardly soluble (or insoluble) in the roughening solution such as acid or oxidizing agent means a relative dissolution rate against the roughening solution such as acid, oxidizing agent or the like. That is, resins with a difference in solubility can optionally be selected as a soluble resin or a hardly soluble resin in the roughening solution such as acid, oxidizing agent or the like. In addition, the means for maintaining the difference in solubility of the resin are not limited to ( 1 ) the type of prepolymer, ( 2 ) the type of hardening agent and ( 3 ) limits the setting of the crosslink density, and other means can be used.

Table 1 shows the prepolymer, curing agent, epoxy equivalent and relative solubility value for each of the above epoxy resins. Table 1

In the invention, the roughening treatment is carried out with the oxidizing agent or the like by making use of the above-mentioned difference in solubility of the epoxy resin for a given time. Such treatment causes the soluble, fine epoxy resin powder to dissolve with a high solubility to the oxidizing agent or the like, thereby forming large recess parts. At the same time, the epoxy resin matrix which contains the thermoplastic resin which is hardly soluble in the oxidizing agent or the like remains, causing a roughened surface (adhesion points) as in 1 shown, is formed.

In the invention, a mixture of thermosetting Resin such as epoxy resin and thermoplastic resin such as PES as a heat-resistant resin matrix used, and in this case the inclusion of the thermoplastic tends Resin to decrease solubility across from the acid, the oxidizing agent or the like. If the resin composite with the quasi-homogeneous, compatible Structure as a heat-resistant resin matrix , the decrease in solubility is particularly striking.

The manufacturing process of using covered with the metal film body according to the invention will be described below.

(1) First, the adhesive according to the invention or mainly from a resin mixture of thermoplastic resin and at least one or two resins from so-called uncured, thermosetting Resins and uncured photosensitive resins, composite adhesives, applied to a support or one by semi-hardening formed film of the adhesive itself is laminated on it, or the carrier itself is formed from the adhesive, creating a layer of the adhesive is formed. Furthermore, the layer of adhesive is dried and hardened, to form an adhesive layer in which the resin composite, which builds up the resin matrix, a quasi-homogeneous, compatible structure, a co-continuous phase structure or a spherical domain structure Has.

Metals, resins, paper can be used as carriers and similar, as mentioned below and they can be converted into a given form.

(Magnetic medium)

Polyethylene terephthalate film, magnetic hard disk

(Electromagnetic shielding)

filter

(Automobile)

Disc brake body, disc brake piston, Coupling hubs,

Oil pump cams, transmission gear shafts

(Industrial machines)

Screw, bearing

(Electrical-electronic Industry)

PCB, plate for mounting of semiconductor components

(Construction materials)

Impregnated with phenolic resin core paper

(2) Then at least part the removable particulate Substance or land-shaped resin in the sea-land structure that disperses in the surface of the adhesive layer is using a roughening solution such as acid, oxidizing agent, alkali, Water, organic solvent or something like that, dissolved and removed, or under conditions of high temperature, high humidity and decomposed and removed under high pressure.

As a method of using the Aufrauungslösung the carrier provided with the adhesive layer is immersed in the roughening solution, or the roughening solution is on the carrier sprayed, causing the surface the adhesive layer can be roughened.

Chromic acid, chromate, Permanganate, ozone, etc. preferred. Hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid and organic acids prefers.

As alkali are sodium hydroxide, Sodium carbonate, potassium hydroxide, ammonium, etc. preferred.

As organic acid are methyl ethyl ketone, Benzene, toluene, dioxane, acetone, trichlorethylene, ethylene dichloride, Carbon disulfide, ethyl acetate, butyl acetate, tetrahydrofuran, Cyclohexanone, nitroethane, pyridine, chloroform, carbon tetrachloride etc.

The relationship between the particulate substance or the land-shaped Resin in the sea-land structure and the roughening solution, which removing it is described below.

The oxidizing agent, such as chromic acid, chromate, Permanganate, ozone or the like, and the acid, like Hydrochloric acid, Nitric acid, Hydrofluoric acid, Sulfuric acid, organic acid or similar, are regarding the heat-resistant resin particles preferred in acid or oxidizing agent soluble are. In particular, amino resin can contain hydrochloric acid contains no heavy metal, as a roughening solution use so that it is practical since the treatment of the waste solution is easy is.

As for elastomers, like rubbery ones Resin and the like , the oxidizing agent, such as chromic acid, is a mixed solution of chromic acid and sulfuric acid, Chromate, permanganate, ozone or the like as a roughening solution prefers.

As a roughening solution for the inorganic powder is hydrofluoric acid preferred over silicon dioxide and aluminum oxide, hydrochloric acid is against carbonates, such as calcium carbonate, sodium carbonate or the like, preferred, and water is against aluminum nitride or the like prefers. About that In addition, aluminum nitride is decomposed by water and gradually oxidized by oxygen in the air so it is necessary the one covered with the metal film body using aluminum nitride with nitrogen or argon during the Protect use.

What is styrene resin under the particulate substance (thermoplastic resin) concerned by dissolution with the organic solvent Methyl ethyl ketone, benzene, toluene, dioxane, acetone, trichlorethylene, ethylene dichloride, Carbon disulfide, ethyl acetate and butyl acetate can be removed as a roughening solution and the organic solvent, such as tetrahydrofuran, cyclohexanone, nitroethane, pyridine or the like, is as a roughening solution for vinyl chloride resin prefers.

(3) Next, the one formed on the carrier roughened surface the adhesive layer is coated with a metal film.

As a method of applying the There is chemical plating, electrolysis plating, sputtering and the like.

As chemical plating, the chemical copper plating, chemical nickel plating, chemical Tin plating, chemical gold plating, chemical silver plating, chemical cobalt-nickel-phosphorus plating, chemical Copper-nickel-phosphorus plating and the like can be called. In particular is at least one method of chemical copper plating that chemical nickel plating, chemical gold plating, the chemical cobalt-nickel-phosphorus plating and chemical copper-nickel-phosphorus plating prefers. About that in addition, the chemically clad layer can be another different one subjected to chemical plating or electrical plating or it can be coated with a solder.

Chemical plating can vary plated patterns by forming a plating resist or the like to be pulled.

Chemical plating can also be carried out via the whole surface carried out and then can be an etching carried out become.

As metal adhered by spraying or the like there is Cu, Ni, Cr, Ti, Mo, Au or an alloy thereof.

It is possible to body coated with a metal film on different parts in the automotive industry, such as disc brake bodies, clutch hub, fuel injection nozzle, fuel transport line, Circuit and the like, and parts in the electrical and electronic industry, such as Lead frame, hermetic sealing, ceramic packaging, ladder, Capacitor, resistor, solar electrode, hard disk and the like, and parts in the field of industrial machines, such as pumps, valves, Heat exchanger, Filter, screw, nozzles, Bearings and the like, apply.

• (1) Zuerst wird eine Verdrahtungsplatte als Träger verwendet, und dann wird der Kleber gemäß der Erfindung oder die sogenannte Harzmischung, die hauptsächlich aus thermoplastischem Harz und ungehärtetem, wärmehärtbarem Harz und/oder ungehärte tem, lichtempfindlichem Harz aufgebaut ist, auf die Verdrahtungsplatte aufgebracht, oder ein Film von halbgehärtetem Kleber selbst wird darauf laminiert, oder die gedruckte Platte selbst wird aus dem Kleber unter Bildung einer Schicht des Klebers hergestellt. Ferner wird die Schicht des Klebers getrocknet und ausgehärtet, um eine Klebeschicht zu bilden, in welchem der Harzverbund, welcher die Harzmatrix aufbaut, eine quasihomogene, verträgliche Struktur, eine co-kontinuierliche Phasenstruktur oder eine kugelförmige Domänenstruktur hat.
• (2) Dann wird wenigstens ein Teil der entfernbaren, teilchenförmigen Substanz, die auf der Oberfläche der Klebeschicht oder dem landförmigen Harz in der Land-Meer-Struktur dispergiert ist, unter Verwendung einer Aufrauungslösung, wie Säure, Oxidationsmittel, Alkali, Wasser, organisches Lösungsmittel oder Ähnliches, aufgelöst und entfernt oder unter Bedingungen hoher Temperatur, hoher Feuchtigkeit und hohem Druck zersetzt und entfernt. Als Verfahren der Anwendung der Aufrauungslösung kann die Verwendung derselben Aufrauungslösung, wie vorher erwähnt, durchgeführt werden, indem die mit der Klebeschicht versehene Verdrahtungsplatte in diese Lösung eingetaucht wird, oder die Aufrauungslösung auf die Verdrahtungsplatte aufgesprüht wird, und somit kann die Oberfläche der Klebeschicht aufgeraut werden.
• (3) Als nächstes wird die aufgeraute Oberfläche der auf der Verdrahtungsplatte gebildeten Klebeschicht einem chemischen Plattieren unterworfen.

The method of manufacturing a printed circuit board as a body coated with a metal film is described below.

• (1) First, a wiring board is used as a support, and then the adhesive according to the invention or the so-called resin mixture mainly composed of thermoplastic resin and uncured thermosetting resin and / or uncured photosensitive resin is applied to the wiring board, or a film of semi-hardened adhesive itself is laminated thereon, or the printed board itself is made from the adhesive to form a layer of the adhesive. Furthermore, the layer of the adhesive is dried and cured to form an adhesive layer in which the resin composite, which builds up the resin matrix, has a quasi-homogeneous, compatible structure, a co-continuous phase structure or a spherical domain structure.
• (2) Then, at least a part of the removable particulate substance dispersed on the surface of the adhesive layer or the land-like resin in the land-sea structure is made using a roughening solution such as acid, oxidizing agent, alkali, water, organic solvent or the like, dissolved and removed or decomposed and removed under conditions of high temperature, high humidity and high pressure. As a method of applying the roughening solution, use of the same roughening solution as mentioned above can be carried out by immersing the wiring plate provided with the adhesive layer in this solution or spraying the roughening solution onto the wiring plate, and thus the surface of the adhesive layer can be roughened ,
• (3) Next, the roughened surface of the adhesive layer formed on the wiring board is subjected to chemical plating.

As chemical plating, it can chemical copper plating, chemical nickel plating, chemical Tin plating, chemical gold plating, chemical silver plating, chemical cobalt-nickel-phosphorus plating, chemical copper-nickel-phosphorus plating and similar to be named. In particular, at least one method is chemical Copper plating, chemical nickel plating, chemical Gold plating, cobalt-nickel-phosphorus chemical plating and chemical Copper-nickel-phosphorus plating preferred. Furthermore the chemically plated layer can be another different subjected to chemical plating or electrical plating or it can be coated with a solder.

At formation of the coated Metal film layer can be electrolysis plating, sputtering or the like additionally can be used for chemical plating.

There is metal to be applied Cu, Ni, Cr, Ti, Mo, Au and alloys thereof.

Chemical plating can be a Wiring patterns by forming a plating resist or the like and performing of plating can be drawn directly.

Alternatively, a circuit can be made by etching the over the entire surface formed chemically plated layer are drawn.

As the printed circuit board thus obtained ( 1 a printed circuit board with a surface printed on one side, obtained by forming a plated resist and a circuit on the carrier through the adhesive layer, 2 ) a printed circuit board printed on both sides, obtained by forming a plated resist and a circuit on both surfaces of the carrier through the adhesive layer and through holes, and ( 3 ) multilayer composite circuit boards obtained by forming a circuit on the carrier provided with the conductor layer (which may have through holes or multiple layers) by interlaminate insulation layer (the above adhesive layer) with through holes in the multilayer state.

(Example 1)

• (1) 65 parts by weight of cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-104S, epoxy equivalent: 220, molecular weight: 5000), 40 parts by weight of polyethersulfone (PES) (manufactured by ICI, trade name: Victrex, molecular weight: 17000), 5 parts by weight of hardening agent imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), 20 parts by weight of rubbery fine resin powder (made from Japan Synthetic Rubber Co., Ltd.) with an average particle size of 5.5 μm and 10 Parts by weight of the fine powder with an average particle size of 0.5 μm mixed and mixed with NMP (normal methylpyrrolidone), while the viscosity is set to 120 centipoise in a homodisper shaker, and then kneaded by three rollers to obtain an adhesive solution. The viscosity at room temperature is 2 to 5 Pa · s.
• (2) The glue solution is placed on an insulating glass epoxy backing that is not covered with a copper foil is provided (manufactured by Toshiba Chemical Co., Ltd.) by means of a roll coater (manufactured by Thermatronics Boeki Co., Ltd.) applied and then at 80 ° C. 2 hours, at 120 ° C 5 hours and at 150 ° C 2 Hours dried and hardened, to form an adhesive layer with a thickness of 20 μm.
• (3) The support provided with the adhesive layer is immersed in an aqueous solution of chromic acid (CrO ₃ , 500 g / l) at 70 ° C for 15 minutes to roughen the surface, and then immersed in a neutral solution (manufactured by Shipley) and washed with water. The roughened surface is Rmax = 10 μm according to JIS-B-0601.
• (4) A palladium catalyst (manufactured by Shipley) is applied to the support provided with the roughened adhesive layer to activate the surface of the adhesive layer, and then a plating resist is formed in a conventional manner, which is incorporated into an additive chemical plating solution of a composition shown in Table 2 is immersed for 11 hours to form a chemically copper-plated layer with a plating thickness of 25 µm, thereby producing a circuit board (cf. 1 ).

Table 2

If only the resin corresponds to the Resin matrix of the adhesive used in the invention among the above Conditions is hardened, shows the resulting hardened Product that it measured resin particles with an average particle size of 0.1 μm by TEM.

When a hardened product is obtained by hardening the resin mixture containing no rubber-like fine resin powder, it also has a peak of the glass transition temperature Tg measured by a viscoelastic test under conditions that the vibration frequency is 6.28 rad / s and the temperature rise rate is 5 ° C / min (cf. 2 ) is.

It is therefore assumed that the resin matrix of the adhesive used in this example has a quasi-homogeneous, compatible structure (cf. 3 ) shows.

(Example 2)

• (1) 70 parts by weight of cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., Han Name: EOCN-103S), 30 parts by weight of polyether sulfone ICI, trade name: (PES) (manufactured by Victrex), 10 parts by weight of an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2PHZ-CN), 20 parts by weight of a spherical fine silica powder (manufactured by Nippon Shokubai Kogyo Co., Ltd.) having an average particle size of 5.5 μm and 10 parts by weight of the fine powder having an average particle size of 0.5 μm are mixed and mixed with NMP solvent while the viscosity is set to 120 centipoise in a homodisper shaker, and then kneaded by three rollers to obtain an adhesive solution.
• (2) The glue solution is placed on an insulating glass epoxy backing that is not covered with a copper foil is provided (manufactured by Toshiba Chemical Co., Ltd.) by means of a roll coater (manufactured by Thermatronics Boeki Co., Ltd.) applied and then at 80 ° C. 3 hours at 120 ° C 3 hours and at 150 ° C 5 Hours dried and hardened, to form an adhesive layer with a thickness of 20 μm.
• (3) The carrier provided with the adhesive layer is in hydrofluoric acid 70 ° C 15 Minutes immersed to roughen the surface of the adhesive layer, which then turns into a neutral solution (manufactured by Shipley) is immersed and washed with water.
• (4) A palladium catalyst (manufactured by Shipley) is manufactured applied to the carrier provided with the roughened adhesive layer, around the surface to activate the adhesive layer. Then a plating resist is made in conventional Way, and thereafter the carrier is in a chemical plating solution for additive immersed for 11 hours with the composition shown in Table 2, to form a chemically copper-plated layer with a thickness of 25 μm, making a circuit board.

If only the resin corresponds to the Resin matrix of the adhesive used in this example among the the above conditions is thermoset, contains the resulting hardened Product resin particles with an average particle size of not more than 0.05 μm, measured by TEM.

If the resin matrix that's not a fine one Contains silicon dioxide powder, hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

Therefore, it is believed that the resin matrix of the adhesive used in this example is a quasi-homogeneous, compatible Structure shows.

(Example 3)

• (1) An epoxy-modified CTBN is made by Mixing butadiene-acrylonitrile copolymer oligomer (CTBN) and epoxy resin bisphenol A type and subsequent heating of the components for 2 hours Obtained 160 ° C.
• (2) 70 parts by weight of bisphenol A type epoxy resin (made by Yuka Shell Co., Ltd., trade name: Epikote 828, epoxy equivalent: 190, molecular weight: 380), 30 parts by weight of polyether sulfone (PES) ICI, (manufactured by trade name: Victrex), 10 parts by weight a curing agent imidazole type (manufactured by Shiko ku Kasei Co., Ltd., trade name: 2E4MZ-CN) and 30 parts by weight of the above epoxy-modified CTBN are mixed and mixed with NMP solvent during the viscosity set to 120 centipoise in a homodisper shaker, and then kneaded by three rollers to make an adhesive solution receive.
• (3) The glue solution is placed on an insulating glass epoxy backing that is not covered with a copper foil is provided (manufactured by Toshiba Chemical Co., Ltd.) by means of a roll coater (manufactured by Thermatronics Boeki Co., Ltd.) applied and then at 80 ° C. 1 hour at 120 ° C 2 hours and at 150 ° C Dried and hardened for 4 hours, to form an adhesive layer with a thickness of 20 μm.
• (4) The support provided with the adhesive layer is immersed in an aqueous solution of chromic acid (CrO ₃ , 500 g / l) at 70 ° C for 15 minutes to roughen the surface of the adhesive layer, which is then in a neutral solution (manufactured by Shipley ) is immersed and washed with water.
• (5) A palladium catalyst (manufactured by Shipley) is manufactured applied to the carrier provided with the roughened adhesive layer, around the surface to activate the adhesive layer. After a plating resist in conventional Way is formed, the carrier in a chemical plating solution for additive with of the composition of Table 2 immersed for 11 hours to obtain a to obtain a chemically copper-plated layer with a thickness of 25 μm, making a circuit board.

If only the resin corresponds to the Resin matrix of the adhesive used in this example among the the above conditions is thermoset, contains the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM.

If the resin matrix that is not rubbery Contains resin, hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

It is therefore believed that the Resin matrix of the adhesive used in this example a quasi-homogeneous, compatible Structure shows.

When the resin matrix is examined by SEM there is a "land structure" of butadiene-acrylonitrile copolymer resin in the sea of resin matrix after curing. That is, if the surface the adhesive layer is treated with the oxidizing agent the parts of the land structure dissolved and removed to roughen the surface.

(Example 4)

It is basically the same procedure repeated as in Example 1 using the following adhesive solution.

The adhesive solution is obtained by mixing of 65 parts by weight of epoxy resin of the ice phenol A type (manufactured from Yuka Shell Co., Ltd., Epikote 828), 35 parts by weight of polyethersulfone (PES) (manufactured by ICI, trade name: Victrex), 5 parts by weight a curing agent imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), 20 parts by weight of rubber-like, fine resin powder (manufactured by Japan Synthetic Rubber Co., Ltd.) with a medium one Particle size of 5.5 μm and 10 Parts by weight of the fine powder with an average particle size of 0.5 μm, add a solvent mixture of dimethylformamide / butyl cellosolve (1/1) to adjust one viscosity of 100 centipoise in a homodisper shaker and subsequent kneading by three rollers.

The hardened product that only through hardening of the resin corresponding to the resin matrix used in this example Adhesive obtained in the same manner as in Example 1 shows that it has a continuous structure of balls, one of which it is believed to be epoxy rich resin with a medium Particle size of 0.2 up to 2 μm (co-continuous phase structure), determined by SEM, after the cut is etched with methylene chloride, which dissolves PES.

(Example 5)

It is basically the same procedure repeated as in Example 1 using the following adhesive solution.

The adhesive solution is obtained by mixing of 50 parts by weight of an ice phenol A type epoxy resin (manufactured from Yuka Shell Co., Ltd., Epikote 828), 50 parts by weight of polyethersulfone (PES) (manufactured by ICI, trade name: Victrex), 5 parts by weight a curing agent imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), 20 parts by weight of rubber-like, fine resin powder (manufactured by Japan Synthetic Rubber Co., Ltd.) with a medium one Particle size of 5.5 μm and 10 Add parts by weight of the fine powder with an average particle size of 0.5 μm of DMF (dimethylformamide) to set a viscosity of 100 Centipoise in a homodisper shaker and subsequent kneading by three rollers.

The cured product, which is obtained only by curing the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example, is found to be spheres which are believed to be epoxy-rich resin with an average particle size of 2- Contain 5 μm, determined by SEM after the cut is etched with methylene chloride, which dissolves PES. The resin matrix is also a so-called sea-land structure (spherical domain structure), with epoxy-rich spheres floating in a PES-rich base (cf. 4 ).

(Example 6)

• (1) A photosensitive, dry film (manufactured by Dupont) is placed on a copper-clad, laminated glass epoxy carrier (manufactured by Toshiba Chemical Co., Ltd.) laminated and with ultraviolet rays exposed through a mask film that matches a given circuit pattern is provided as a picture. Then the pattern with 1,1,1-trichloroethane developed, and copper is removed from the non-conductive part with a copper chloride etching solution, and then the dry film is stripped with methylene chloride. Consequently is a circuit board with a first circuit made up of several Ladder patterns on the carrier exists.
• (2) To an alumina particle obtained by dispersing 200 g of alumina particles (manufactured by Nippon Light Metal Co., Ltd., trade name: AX34, average particle size: 3.9 µm) in 5 liters of acetone, a suspension is added dropwise, obtained by dispersing 300 g of alumina powder (manufactured by Nippon Light Metal Co., Ltd., trade name: AX34, average particle size: 0.5 μm) in an acetone solution of 30 g of epoxy resin (manufactured by Mitsui Petroleum Chemical Co., Ltd.) in 1 liter Acetone with stirring in a Henschel mixer, whereby the alumina powder adheres to the surfaces of the alumina particles. After the acetone is removed, the mixture turns on Heated at 150 ° C to form artificial alumina particles. The artificial particles have an average particle size of about 4.3 μm, with about 75% by weight thereof being in a range of ± 2 μm around the mean value of the particle size.
• (3) 70 parts by weight of 50% acrylated product of cresol novolak type epoxy resin (manufactured by Yuka Shell Co., Ltd., epoxy equivalent: 210, molecular weight 2000), 30 parts by weight of polyethersulfone (PES), 15 parts by weight of diallyl terephthalate, 4 parts by weight 2-Methyl-1- [4- (methylthio) phenyl] morpholinopropanone-1 (manufactured by Ciba Geigy) and 4 parts by weight of an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN) are included 50 parts by weight of those in the previous paragraph ( 2 ) produced artificial alumina particles, mixed with butyl cellosolve to adjust the viscosity to 250 centipoise in a homodisper shaker, and then kneaded by three rollers to prepare a photosensitive adhesive solution.
• (4) The light-sensitive adhesive solution is applied to the 1 ) printed circuit board produced by means of a roller coater, left in the horizontal state for 20 minutes and dried at 70 ° C to form a light-sensitive adhesive layer with a thickness of about 50 microns.
• (5) The in paragraph ( 4 ) treated circuit board is sealed with a photomask film, which is printed with black circles with a diameter of 100 μm, which is exposed with a super high pressure mercury lamp of 500 mJ / cm ² . It is then subjected to ultrasonic development with a solution of DMDG (diethylene glycol dimethyl ether) to form openings as through holes with a diameter of 100 μm on the plate. Furthermore, the circuit board is exposed with a super high pressure mercury lamp of about 3000 mJ / cm ² and then subjected to a heat treatment at 100 ° C for 1 hour and at 150 ° C for 5 hours to form an adhesive layer with an opening corresponding to the photomask film in an excellent To form dimensional accuracy.
• (6) The in paragraph ( 5 ) treated circuit board is treated with hydrofluoric acid and immersed in potassium permanganate (KMnO ₄ , 500 g / l) at 70 ° C for 15 minutes to roughen the surface of the adhesive layer, which is then immersed in a neutral solution (manufactured by Shipley) and with water is washed.
• (7) A palladium catalyst (manufactured by Shipley) is manufactured applied to the plate provided with the roughened adhesive layer, around the surface to activate the adhesive layer, and then in a chemical plating solution for additive immersed with the composition of Table 2 for 11 hours to obtain a chemically copper-plated layer with a thickness of 25 μm.
• (8) The steps of paragraphs ( 4 ) - ( 7 ) are repeated twice, and further the step of paragraph ( 1 ) to produce a multi-layer circuit board in which the wiring layers 4 are (cf. 5 ).

It is noted that the cured product obtained by merely curing the resin according to the resin matrix of the adhesive used in this example under the above conditions has a continuous structure of spheres which are believed to be epoxy-rich resin with a medium particle size of 0.2–2 μm (co-continuous phase structure), observed with SEM after the cut is etched with methylene chloride (cf. 6 ).

Furthermore, the cured product obtained by curing the mixture of the resin composition without the above artificial alumina particles has two peaks of the glass transition temperature Tg measured by the viscoelastic measurement test under the conditions of an oscillation frequency of 6.28 rad / s and a temperature rising rate of 5 ° C / s (cf. 7 ).

Therefore, it is believed that the resin matrix of the adhesive used in this example is co-continuous Has phase structure.

(Example 7)

• (1) A photosensitive, dry film (manufactured by DuPont) is placed on a copper-clad, laminated glass epoxy carrier (manufactured by Toshiba Chemical Co., Ltd.) laminated and with ultraviolet rays exposed through a mask film that matches a given circuit pattern is provided as a picture. Then the pattern with 1,1,1-trichloroethane developed, and copper is removed from the non-conductor part with a copper chloride containing etching solution removed, and then the dry film is peeled off with methylene chloride. Consequently is a circuit board with a first circuit, consisting of several conductor patterns on the carrier.
• (2) Epoxy oligomer (CNA25, molecular weight: 4000) of cresol novolak type epoxy resin dissolved in DMDG (diethylene glycol dimethyl ether) in which 25% of the epoxy groups are acrylated to obtain photosensitivity, PES (molecular weight: 17000), a curing agent of Imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer and a photoini Tiator (manufactured by Ciba Geigy, trade name: 1-907) are mixed in NMP solvent according to the following composition and mixed with 20 parts by weight of rubbery fine resin powder (manufactured by Japan Synthetic Rubber Co., Ltd.) having an average particle size of 5 , 5 µm and 10 parts by weight of the powder having an average particle size of 0.5 µm to adjust the viscosity to 120 centipoise in a homodisper shaker, and then kneaded by three rollers to obtain a photosensitive adhesive solution. Resin composition: photosensitive epoxy / PES / M215 / 1-907 / imidazole = 75/25/10/5/5/5
• (3) The photosensitive adhesive solution is applied to the solution described in paragraph ( 1 ) printed circuit board produced by means of a roller coater, left in the horizontal state for 20 minutes and dried at 60 ° C.
• (4) The in paragraph ( 3 ) treated circuit board is sealed with a photomask film, which is printed with black circles with a diameter of 100 μm, which is exposed with a super high pressure mercury lamp of 500 mJ / cm ² . It is subjected to an ultrasonic treatment with a DMDG solution to form through holes with a diameter of 100 μm on the plate. Furthermore, the printed circuit board is exposed to a super high pressure mercury lamp of approximately 3000 mJ / cm ² and subjected to a heat treatment at 100 ° C. for 1 hour and at 150 ° C. for 5 hours to form an adhesive layer of 50 μm thick with an opening corresponding to the photomask film to form in excellent dimensional accuracy.
• (5) The in paragraph ( 4 ) treated circuit board is immersed in potassium permanganate (KMnO ₄ , 500 g / l) at 70 ° C for 15 minutes to roughen the surface of the adhesive layer, which is then immersed in a neutral solution (manufactured by Shipley) and washed with water.
• (6) A palladium catalyst (manufactured by Shipley) is manufactured applied to the plate provided with the roughened adhesive layer, around the surface to activate the adhesive layer, and then in a chemical plating solution for additive immersed with the composition of Table 2 for 11 hours to obtain a chemically copper-plated layer with a thickness of 25 μm.
• (7) The steps of paragraphs ( 3 ) - ( 6 ) are repeated twice, and further the step of paragraph ( 1 ) to produce a multi-layer circuit board in which the wiring layers 4 are.

It is found that the hardened product, obtained by drying, UV curing and heat hardening of only the resin corresponding to the resin matrix in this example used adhesive, resin particles under the above conditions with an average particle size of not more than 0.1 μm contains determined by TEM in the same manner as in Example 1.

Furthermore, the hardened product, obtained by hardening the mixture of the resin composition which is not the above contains rubber-like, fine resin powder, a peak of the glass transition temperature Tg, measured by the viscoelastic measurement test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

It is therefore assumed that the resin matrix of the adhesive used in this example has a quasi-homogeneous, compatible structure (cf. 3 ).

In addition, SEM photographs of sections of the adhesive layer before and after curing in the 8th and 9 shown.

(Example 8)

The same procedure as in example 7 basically repeated using the following adhesive solution.

A photosensitive adhesive solution is obtained by mixing epoxy oligomer (CNA25, molecular weight: 4000) of cresol novolak type epoxy resin in which 25% of the epoxy groups are acrylated to give photosensitivity, PES (molecular weight: 17000), a curing agent of Imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer and a photoinitiator (manufactured by Ciba Geigy, Trade name: 1-907) according to the following composition in NMP (dimethylformamide) solvent and mixing with 20 parts by weight of rubbery fine resin powder (manufactured by Japan Synthetic Rubber Co., Ltd.) having an average particle size of 5.5 μm and 10 Parts by weight of the powder with an average particle size of 0.5 μm to reduce the viscosity to 120 centipoise in a homodisper-Sch ttelmaschine set, and then kneading through three rolls.
Resin composition: photosensitive epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5

The curing of the adhesive is done by Drying at 80 ° C, UV curing and subsequent Heat curing performed.

It is found that the hardened product, obtained by just hardening of the resin corresponding to the resin matrix used in this example Adhesive has a continuous structure under the above conditions of bullets that are believed to be epoxy rich Resin with an average particle size of 0.2–2 μm (co-continuous phase structure) have determined by SEM after the cut with methylene chloride etched is.

(Example 9)

The same procedure as in example 7 basically performed using the following adhesive solution.

A photosensitive adhesive solution is obtained by mixing epoxy oligomer (CNA25, molecular weight: 4000) of cresol novolak type epoxy resin in which 25% of the epoxy groups are acrylated to give photosensitivity, PES (molecular weight: 17000), an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer, and a photoinitiator (manufactured by Ciba Geigy, trade name : 1-907) according to the following composition in NMP (dimethylformamide) solvent and mixing with 20 parts by weight of rubber-like, fine resin powder with an average particle size of 5.5 μm and 10 parts by weight of the powder with an average particle size of 0.5 μm, to adjust the viscosity to 120 centipoise in a homodisper shaker and then kneading n by three rollers.
Resin composition: photosensitive epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5

The curing of the adhesive is done by Drying at 100 ° C, UV curing and subsequent Heat curing performed.

It is found that the hardened product, obtained by hardening of only the resin corresponding to the resin matrix of the one in it Example used glue in the same way as in Example 1 Balls are believed to be epoxy-rich resin with an average particle size of 2-5 μm, determined by SEM after the cut with methylene chloride, which PES dissolves, is etched. The resin matrix also has a so-called sea-land structure (spherical Domain structure), where float epoxy-rich balls in a PES-rich base.

From Example 7 to Example 9 approved been that hardened Product with the quasi-homogeneous, compatible structure, the co-continuous Phase structure or spherical Preserve domain structure is made from the adhesive with the same composition by varying the drying conditions. If the photosensitive adhesive has a homogeneous structure at the time of drying, namely drying quickly through photo curing carried out, and thus there is no relative phase separation by the subsequent one Heat curing.

In addition, the phase diagram in the 10 - 12 shown for reference. These phase diagrams are obtained using photosensitive epoxy / PES / TMPTA / I-907 / imidazole = 75/25 / 20/5/5, which is different from the manufacturing conditions of the adhesive in Examples 7-9.

(Example 10)

The same procedure as in example 7 basically repeated using the following adhesive solution.

A photosensitive adhesive solution is obtained by mixing epoxy oligomer (manufactured by Yuka Shell Co., Ltd.) of cresol novolak type epoxy resin in which 100% of the epoxy groups are acrylated to give photosensitivity, PES, an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer, and a photoinitiator (manufactured by Ciba Geigy, trade name : I-907) according to the following composition in NMP (dimethylformamide) solvent and mixing with 20 parts by weight of rubbery fine resin powder (manufactured by Japan Synthetic Rubber Co., Ltd.) having an average particle size of 5.5 µm and 10 parts by weight of the powder with an average particle size of 0.5 μm to adjust a viscosity to 120 centipoise in a homodisper spout machine and subsequent kneading by three rollers.
Resin composition: photosensitive epoxy / PES / M215 / I-907 / imidazole = 80/20/10/5/5

If only the resin corresponds to the Resin matrix of the adhesive used in this example in the same Hardened as in Example 7 will contain the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM in the same way as in Example 1.

If the resin mixture containing no plastic-like resin is cured, one will continue to Peak of glass transition temperature Tg obtained, measured by a viscoelastic test under the conditions of an oscillation frequency of 6.28 rad / s and a temperature rise rate of 5 ° C / min.

It is therefore assumed that the resin matrix of the adhesive used in this example shows a quasi-homogeneous, compatible structure (cf. 3 ).

(Example 11)

The same procedure as in example 7 basically repeated using the following adhesive solution.

A photosensitive adhesive solution is obtained by mixing epoxy oligomer (manufactured by Yuka Shell Co., Ltd.) of cresol novolak type epoxy resin in which 100% of the epoxy groups are acrylated to give photosensitivity, phenoxy resin, an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer, and a photoinitiator (manufactured by Ciba Geigy, trade name : I-907) according to the following composition in DMF and mixing with 30 parts by weight of aggregated, rubbery, fine resin powder with an average particle size of 3.5 μm (cf. the production process described in Example 1 of JP-A-1-301775) for setting a viscosity of 120 centipoise in a homodisper shaker while DMF solvent is added, and then pouring kneading by three rollers.
Resin composition: photosensitive epoxy / phenoxy / M215 / I-907 / imidazole = 79/30/10/5/5

It is found that the hardened product, obtained by hardening of only the resin corresponding to the resin matrix of the one in it Example used glue in the same way as in Example 7 has a continuous structure of spheres, of which adopted is that it is epoxy-rich resin with an average particle size of 0.2-2 μm (co-continuous Phase structure) determined by SEM after the cut with 2-butanone, which dissolves the phenoxy resin, is etched.

(Example 12)

The same procedure as in example 7 basically repeated using the following adhesive solution.

A photosensitive adhesive solution is obtained by mixing epoxy oligomer (manufactured by Yuka Shell Co., Ltd.) of cresol novolak type epoxy resin in which 100% of the epoxy groups are acrylated to give photosensitivity, PSF, an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer, and a photoinitiator (manufactured by Ciba Geigy, trade name : 1-907) according to the following composition in DMF and mixing with 30 parts by weight of aggregated, rubbery, fine resin powder with an average particle size of 3.5 μm (cf. the production process described in Example 1 of JP-A-1-301775) to adjust a viscosity of 120 centipoise in a homodisper shaker while adding DMF solvent and then s Kneading with three rollers.
Resin composition: photosensitive epoxy / PSF / M215 / I-907 / imidazole = 60/40/10/5/5

It is found that the hardened product, obtained by hardening of only the resin corresponding to the resin matrix of the one in it Example used glue in the same way as in Example 7, Balls are believed to be epoxy-rich resin with an average particle size of 2-5 μm, determined by SEM after the cut with methylene chloride, which PSF dissolves, is etched. The resin matrix also has a so-called sea-land structure (spherical Domain structure), wherein float epoxy-rich balls in a PES-rich base.

(Example 13)

The same procedure as in example 5 basically repeated with the exception that zirconia (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name: NS-OY-S) instead of the rubbery fine resin powder is used, and that Hydrofluoric acid used as a roughening solution becomes.

In addition, the resin structure the resin matrix of the adhesive used in this example has a spherical domain structure.

(Example 14)

The same procedure as in example 8 basically repeated with the exception that magnesium oxide (manufactured by Iwatani Kagaku Kogyo Co., Ltd., trade name: MTK-30) instead of the rubbery fine resin powder is used, and that 6 N hydrochloric acid used as a roughening solution becomes.

In addition, the resin structure the resin matrix of the adhesive used in this example is co-continuous Phase structure.

(Example 15)

The same procedure as in example 9 basically repeated with the exception that aluminum hydroxide (manufactured from Nippon Keikogyo Co., Ltd., trade name: B103 · T) instead of the rubbery fine resin powder is used, and that an aqueous ammonia solution as a roughening solution is used.

In addition, the resin structure the resin matrix of the adhesive used in this example has a spherical domain structure.

(Example 16)

The same procedure as in example 4 basically repeated using the following adhesive solution.

An adhesive solution is obtained by mixing of butadiene-acrylonitrile copolymer oligomer (CTBN) with epoxy resin from bisphenol A type, heating to 160 ° C for 2 hours to form an epoxy-modified CTBN, mixing 30 parts by weight the resin solution obtained with 65 parts by weight of bisphenol A type epoxy resin (made from Yuka Shell Co., Ltd., Epikote 828), 35 parts by weight of polyethersulfone (PES) (manufactured by ICI, trade name: Victrex) and 5 parts by weight a curing agent imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), adjusting the viscosity to 120 centipoise in one Homodisper shaker, while the addition of a solvent mixture of dimethylformamide / butyl cellosolve (1/1) and then kneading by three rollers.

It is found that the hardened product, obtained by hardening of only the resin corresponding to the resin matrix of the one in it Example used glue in the same way as in Example 4 has a continuous structure of spheres, of which adopted is that it is epoxy-rich resin with an average particle size of 0.2-2 μm (co-continuous Phase structure) determined by SEM after the cut with Methylene chloride, which dissolves PES, is etched.

Furthermore, SEM determines that a "land structure" of butadiene-acrylonitrile copolymer rubber resin is in a sea of resin matrix.

(Example 17)

The same procedure as in example 5 basically repeated using the following adhesive solution.

An adhesive solution is obtained by mixing of butadiene-acrylonitrile copolymer oligomer (CTBN) with epoxy resin from bisphenol A type, heating to 160 ° C for 2 hours to form an epoxy-modified CTBN, mixing 30 parts by weight the resin solution obtained with 50 parts by weight of bisphenol A type epoxy resin (made from Yuka Shell Co., Ltd., Epikote 828), 50 parts by weight of polyethersulfone (PES) (manufactured by ICI, trade name: Victrex) and 5 parts by weight a curing agent imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), adjusting the viscosity to 100 centipoise in one Homodisper shaker while the addition of DMF and subsequent Knead using three rollers.

It is found that the cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 5 has spheres which are believed to be epoxy-rich resin with an average particle size of Contain 2-5 μm, determined by SEM, after the cut is etched with methylene chloride, which dissolves PES. This resin matrix is a so-called sea-land structure (spherical domain structure) in which epoxy-rich spheres float in a PES-rich base (cf. 4 ).

Furthermore, SEM determines that a "land structure" of butadiene-acrylonitrile copolymer rubber resin is in a sea of resin matrix.

(Example 18)

The same procedure as in example 7 basically repeated using the following adhesive solution.

An adhesive solution is obtained by mixing butadiene-acrylonitrile copolymer oligomer (CTBN) with ice phenol A type epoxy resin, heating at 160 ° C for 2 hours to form an epoxy-modified CTBN, mixing 30 parts by weight of the resulting resin solution with epoxy oligomer of novolak type epoxy resin dissolved in DMDG in which 25% of the epoxy groups are acrylated to give photosensitivity (CNA 25, molecular weight: 4000), PES (molecular weight: 17000), an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer, benzophenone (manufactured by Kanto Kagaku Co., Ltd.) as a photoinitiator and Michler's ketone (manufactured by Kanto Kagaku Co., Ltd.) as a photosensitizer according to the following composition in NMP, adjusting the viscosity to 120 centipoise in a homodisper shaker and then kneading with three rollers.
Resin composition: photosensitive epoxy / PES / M215 / BP / imidazole = 75/25/10/5 / 0.5 / 5

If only the resin corresponds to the Resin matrix of the adhesive used in this example in the same Hardened as in Example 7 will contain the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM in the same way as in Example 1.

If that's not a rubbery resin containing resin mixture hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions an oscillation frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

It is therefore assumed that the resin matrix of the adhesive used in this example shows a quasi-homogeneous, compatible structure (cf. 3 ).

SEM also determines that a "land structure" of butadiene-acrylonitrile copolymer rubber resin is in a sea of resin matrix.

(Example 19)

The same procedure as in example 8 basically repeated using the following adhesive solution.

An adhesive solution is obtained by mixing butadiene-acrylonitrile copolymer oligomer (CTBN) with ice phenol A type epoxy resin, heating at 160 ° C for 2 hours to form an epoxy-modified CTBN, mixing 30 parts by weight of the resulting resin solution with epoxy oligomer of novolak type epoxy resin dissolved in DMDG in which 25% of the epoxy groups are acrylated to give photosensitivity (CNA 25, molecular weight: 4000), PES (molecular weight: 17000), an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer and a photoinitiator (manufactured by Ciba Geigy, trade name: I-907) according to the following composition in DMF, adjusting the viscosity to 120 centipoise in a homodisper shaker and then kneading by three Rollers.
Resin composition: photosensitive epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5

It is found that the hardened product, obtained by hardening of only the resin corresponding to the resin matrix of the one in it Example used glue in the same way as in Example 8 has a continuous structure of spheres, assuming that they have epoxy-rich resin with an average particle size of 0.2-2 μm (co-continuous Phase structure) determined by SEM after the cut with Etched methylene chloride is.

Furthermore, SEM determines that a "land structure" of butadiene-acrylonitrile copolymer rubber resin is in a sea of resin matrix.

(Example 20)

The same procedure as in example 9 basically repeated using the following adhesive solution.

An adhesive solution is obtained by mixing butadiene-acrylonitrile copolymer oligomer (CTBN) with ice phenol A type epoxy resin, heating at 160 ° C for 2 hours to form an epoxy-modified CTBN, mixing 30 parts by weight of the resulting resin solution with epoxy oligomer of novolak type epoxy resin dissolved in DMDG in which 25% of the epoxy groups are acrylated to give photosensitivity (CNA 25, molecular weight: 4000), PES (molecular weight: 17000), a hard Imidazole type agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer and a photoinitiator (manufactured by Ciba Geigy, trade name: I-907) according to the following composition in DMF, adjusting the viscosity to 120 centipoise in a homodisper shaker and then kneading by three rollers.
Resin composition: photosensitive epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5

It is found that the hardened product, obtained by hardening of only the resin corresponding to the resin matrix of the one in it Example used glue in the same way as in Example 9 Spheres, which is believed to contain epoxy-rich resin have an average particle size of 2-5 μm, determined by SEM after the cut with methylene chloride, which Dissolves PES, etched is. This resin matrix is a so-called sea-land structure (spherical domain structure), in which epoxy-rich spheres float in a PES-rich foundation.

Furthermore, SEM determines that a "land structure" of butadiene-acrylonitrile copolymer rubber resin is in a sea of resin matrix.

(Example 21)

The same procedure as in example 7 basically repeated using the following adhesive solution.

An adhesive solution is obtained by mixing epoxy oligomer of novolak type epoxy resin in which 25% of the epoxy groups are acrylated to give photosensitivity (CNA 25, molecular weight: 4000), PES (molecular weight: 17000), an imidazole type curing agent ( manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer and a photoinitiator (manufactured by Ciba Geigy, trade name: I-907) according to the following composition in DMF, mixing the resulting mixture with 25 parts by weight of silicone resin with epoxy group ends, adjusting the viscosity to 120 centipoise in a homodisper shaker and then kneading by three rollers.
Resin composition: photosensitive epoxy / PES / M215 / I-907 / imidazole = 70/30/10/5/5

If only the resin corresponds to the Resin matrix of the adhesive used in this example in the same Hardened as in Example 7 will contain the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM in the same way as in Example 1.

If the resin mixture, which is not a silicone resin with epoxy group ends, hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

Therefore, it is believed that the resin matrix of the adhesive used in this example is a quasi-homogeneous, compatible Structure shows.

(Example 22)

• (1) 65 parts by weight of cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-104S, epoxy equivalent: 220, molecular weight: 5000), 40 parts by weight of polyethersulfone (PES) (manufactured by ICI, trade name: Victrex, molecular weight: 17000), 5 parts by weight of hardening agent imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), 20 parts by weight of melamine resin powder with a low degree of crosslinking and an average particle size of 5.5 μm and 10 Parts by weight of the same powder with an average particle size of 0.5 microns mixed and mixed with NMP, while the viscosity in a Homodisper shaker is set to 120 centipoise, and then by three rollers to get an adhesive solution kneaded. In this case is the viscosity at room temperature 2 to 5 Pa · s.
• (2) The glue solution will on both surfaces an insulating glass-epoxy carrier applied, which was left in the horizontal state for 20 minutes and then at 60 ° C dried and by heating to 100 ° C for 1 hour and to 150 ° C for 5 hours hardened to form a resin adhesive layer with a thickness of about 50 μm.
• (3) The support provided with the adhesive layers on both surfaces is left in saturated steam at 121 ° C and a pressure of 2 atmospheres for 2 hours to decompose and remove melamine resin powder on the surface of the adhesive layer. Electron microscopic photographs (SEM) before and after removal by decomposition are in 13 respectively. 14 shown. As can be seen from these photographs, the melamine resin becomes low due to the decomposition.
• (4) A palladium catalyst (manufactured by Shipley) is manufactured on the carrier with the roughened surface of the insulating resin layer applied to the surface of the to activate the insulating layer and then into a chemical Copper plating solution 11 hours immersed to a chemically copper-plated layer with a thickness of 25 μm to obtain, whereby a copper-clad on both surfaces, laminated carrier will be produced.
• (5) through holes are in the laminated carrier educated.
• (6) A palladium core (manufactured by Shipley) is applied and then a photoresist is applied that exposes to light and is developed to form a plating resist.
• (7) Chemical copper plating becomes more common Performed way and then electrical copper plating is performed to to form a circuit part.
• (8) After the plating resist is peeled off, an etch with Iron (III) chloride carried out, to remove the copper film between the patterns to thereby to manufacture a printed circuit board.

If only the resin corresponds to the Resin matrix of the adhesive used in this example among the the above conditions is thermoset, contains the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM in the same way as in Example 1.

If the resin matrix, which no Contains melamine resin powder, hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

It is therefore assumed that the resin matrix of the adhesive used in this example shows a quasi-homogeneous, compatible structure (cf. 3 ).

(Example 23)

The same procedure as in example 7 basically repeated using the following adhesive solution.

An adhesive solution is obtained by mixing epoxy oligomer of cresol novolak type epoxy resin in which 25% of the epoxy groups are acrylated to give photosensitivity (CNA 25, molecular weight: 4000), PES (molecular weight: 17000), a curing agent of Type of imidazole (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), an acrylated isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M215) as a photosensitive monomer; Benzophenone (BP) as a photo initiator (manufactured by Kanto Kagaku Co., Ltd.) and Michler's ketone as a photosensitizer (manufactured by Kanto Kagaku Co., Ltd.) according to the following composition in DMDG, adding powder of cellulose acetate butyrate, adjusting the viscosity 120 centipoise in a homodisper shaker with NMP and subsequent kneading by three rollers.
Resin composition: photosensitive epoxy / PES / M215 / BP / imidazole = 75/25/10/5 / 0.5 / 5

In addition, the roughening by immersion in an aqueous solution of 1 M sodium hydroxide at 80 ° C carried out, to hydrolyze cellulose acetate butyrate.

If only the resin corresponds to the Resin matrix of the adhesive used in this example in the same Hardened as in Example 7 will contain the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM in the same way as in Example 1.

If the resin mixture that is not rubbery Contains resin, hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

Therefore, it is believed that the resin matrix of the adhesive used in this example is a quasi-homogeneous, compatible Structure shows.

In those prepared in Examples 1-23 Printed circuit boards become the peel strength the chemical copper-plated layer, the insulation resistance and the glass transition temperature Tg of the interlaminar insulating resin layer measured. Further a heat cycle test is carried out at –65 ° C × 30 min up to 125 ° C × 30 min carried out. The measured results are shown in Table 3. How out The results of this table can be seen, printed circuit boards with considerable improved adhesive strength, insulating properties, heat resistance and thermal cycle property by using the adhesive according to the invention in which the resin composite, which is a quasi-homogeneous, compatible Structure, a co-continuous phase structure or a spherical domain structure has, is used as a resin matrix.

Table 3

In addition, the reviews the peel strength, insulation resistance, glass transition temperature Tg and Heat cycle test and the evaluation described below.

(1) peel strength

It is measured according to JIS-C-6481.

(2) insulation resistance

A resist pattern is made by forming an interlaminar insulating layer on the carrier, roughening the carrier, applying a catalyst and subsequent Forming a plating resist. After that, a chemical Plating done and the insulation resistance between patterns is measured. In In this case, the value of the insulation resistance between patterns in a comb type pattern of L / S = 75/75 μm after 1000 hours at 80 ° C / 85% / 24 V measured.

(3) Glass transition temperature Tg

It is characterized by the dynamic viscoelastic Measurement measured.

(4) Thermal cycle test

It is at -65 ° C × 30 min to 125 ° C × 30 min carried out, Meanwhile the appearance of cracks and detachment the interlaminar insulating layer can be measured. It is through the durable cycle number is rated.

(Example 24) Metallic decorative melamine laminate

• (1) Ein Melaminharz wird in einer Papierherstellungsfolie von holzigen Pulpefasern mit einem Flächengewicht von 10–80 g/m² imprägniert und getrocknet, um ein imprägniertes Papier mit einer Dicke von 100 μm zu bilden.
• (2) 65 Gewichtsteile Epoxyharz vom Kresol-Novolak-Typ (hergestellt von Nippon Kayaku Co., Ltd., Handelsbezeichnung: EOCN-104S, Epoxyäquivalent: 220, Molekulargewicht: 5000), 40 Gewichtsteile Polyethersulfon (PES) (hergestellt von ICl, Handelsbezeichnung: Victrex, Molekulargewicht: 17000), 5 Gewichtsteile Härtungsmittel vom Imidazoltyp (hergestellt von Shikoku Kasei Co., Ltd., Handelsbezeichnung: 2E4MZ-CN), 20 Gewichtsteile feines Pulver von Calciumcarbonat mit einer mittleren Teilchengröße von 5,5 μm und 10 Gewichtsteile des gleichen feinen Pulvers mit einer mittleren Teilchengröße von 0,5 μm werden vermischt und mit einer Lösungsmittelmischung von Dimethylformamid/Butylcellosolve (1/1) versetzt, währenddessen die Viskosität auf 120 Centipoise in einer Homodisper-Schüttelmaschine eingestellt wird, und dann durch drei Walzen zum Erhalt einer Kleberlösung verknetet. In diesem Fall beträgt die Viskosität bei Raumtemperatur 2 bis 5 Pa·s.
• (3) Der im Absatz (2) erhaltene Kleber wird auf eine Oberfläche eines Sperrholzes aufgebracht, welcher unter vermindertem Druck bei 30°C getrocknet und durch Erwärmen auf 80°C für 2 Stunden, auf 120°C für 5 Stunden und auf 150°C für 2 Stunden gehärtet wird, um eine Klebeschicht mit einer Dicke von 20 μm zu bilden.
• (4) Die Klebeschicht wird in 6 N Chlorwasserstoffsäure bei 70°C 15 Minuten eingetaucht, um die Oberfläche der Klebeschicht aufzurauen, die in eine neutrale Lösung (hergestellt von Shipley) eingetaucht und mit Wasser gewaschen wird, um eine Klebeschicht mit Rmax = 10 ± 5 μm zu erhalten.
• (5) Ein Palladiumkatalysator (hergestellt von Shipley) wird auf den mit der aufgerauten Klebeschicht versehenen Trager aufgebracht, um die Oberfläche der Klebeschicht zu aktivieren, die einem chemischen Silberplattieren in üblicher Weise unterworfen wird, um eine Silberschicht mit einer Dicke von 60 μm auf der Oberfläche zu bilden.
• (6) Das im Absatz (1) erhaltene imprägnierte Melaminharzpapier wird auf die Oberfläche der Silberschicht als Überzugspapier laminiert.
• (7) Eine Formungsplatte mit Unebenheiten von 1–60 μm wird auf das Überzugspapier laminiert und bei 130–170°C unter einem Druck von 30–80 kg/cm² heißgepresst, um ein dekoratives Melaminlaminat mit geprägter Oberfläche und metallischem Glanz zu erhalten.

Although Examples 1-25 describe the embodiments of the circuit board, the invention is applied to a decorative laminate in this example.

• (1) A melamine resin is impregnated in a papermaking sheet of woody pulp fibers with a basis weight of 10-80 g / m ² and dried to form an impregnated paper with a thickness of 100 µm.
• (2) 65 parts by weight of cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-104S, epoxy equivalent: 220, molecular weight: 5000), 40 parts by weight of polyethersulfone (PES) (manufactured by ICl, trade name : Victrex, molecular weight: 17000), 5 parts by weight of imidazole type hardener (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), 20 parts by weight of fine powder of calcium carbonate with an average particle size of 5.5 μm and 10 parts by weight of same fine powder with an average particle size of 0.5 μm are mixed and mixed with a solvent mixture of dimethylformamide / butyl cellosolve (1/1), while the viscosity is adjusted to 120 centipoise in a homodisper shaker, and then by three rollers to obtain kneaded with an adhesive solution. In this case the viscosity at room temperature is 2 to 5 Pa · s.
• (3) The adhesive obtained in paragraph (2) is applied to a surface of a plywood which is dried under reduced pressure at 30 ° C and by heating at 80 ° C for 2 hours, at 120 ° C for 5 hours and at 150 ° C is cured for 2 hours to form an adhesive layer with a thickness of 20 μm.
• (4) The adhesive layer is immersed in 6N hydrochloric acid at 70 ° C for 15 minutes to roughen the surface of the adhesive layer, which is immersed in a neutral solution (manufactured by Shipley) and washed with water to form an adhesive layer with Rmax = 10 ± 5 μm.
• (5) A palladium catalyst (manufactured by Shipley) is applied to the carrier provided with the roughened adhesive layer to activate the surface of the adhesive layer, which is subjected to chemical silver plating in the usual manner to cover a silver layer with a thickness of 60 μm on the To form surface.
• (6) The impregnated melamine resin paper obtained in paragraph (1) is laminated on the surface of the silver layer as a coating paper.
• (7) A molding plate with unevenness of 1-60 µm is laminated on the cover paper and hot pressed at 130-170 ° C under a pressure of 30-80 kg / cm ² to obtain a decorative melamine laminate with an embossed surface and metallic luster.

Since the melamine resin layer with a easily transferable and uneven surface is formed on the decorative melamine laminate Roughness as a lens, floating around the underground silver layer to see what makes the silver shine attractive and the design excellent becomes.

In addition, cracking or a peel in the decorative active laminate even after the thermal cycle test from -65 ° C × 30 min to 125 ° C × 30 min not observed.

If only the resin corresponding to the resin matrix of the adhesive used in this example is cured under the above conditions, the resulting cured product contains resin particles having an average particle size of not more than 0.1 µm, measured by TEM in the same manner as in Example 1.

If the resin matrix that's not a fine one Contains powder of calcium carbonate hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

Therefore, the resin matrix of the in In this example, glue was used as a quasi-homogeneous, compatible structure viewed having.

(Example 25) Plated coated gear

• (1) Ein Getriebeformkörper wird unter Verwendung eines Polyimids in gewöhnlicher Weise hergestellt.
• (2) Eine Kleberlösung wird erhalten durch Vermischen von Epoxyoligomer von Epoxyharz vom Kresol-Novolak-Typ, in welchem 25% der Epoxygruppen acryliert sind, um eine Fotoempfindlichkeit zu ergeben (CNA 25, Molekulargewicht: 4000), PES (Molekulargewicht: 17000), einem Härtungsmittel vom Imidazoltyp (hergestellt von Shikoku Kasei Co., Ltd., Handelsbezeichnung: 2E4MZ-CN) mit Caprolacton modifiziertem Trisisocyanurat (hergestellt von Toa Gosei Co., Ltd., Handelsbezeichnung: Aronics M315) als fotoempfindliches Monomer, Benzophenon (BP) als Fotoinitiator und Michlers Keton als Fotosensibilisierer gemäß der folgenden Zusammensetzung in DMDG, Versetzen mit 30 Gewichtsteilen Kautschukfüllstoff (hergestellt von Japan Synthetic Rubber Co., Ltd.) mit einer mittleren Teilchengröße von 5,0 μm, Einstellen der Viskosität auf 1000 Centipoise in einer Homodisper-Schüttelmaschine mit NMP und anschließendes Verkneten durch drei Walzen. Harzzusammensetzung: fotoempfindlich gemachtes Epoxy/PES/M315/BP/ Imidazol = 70/30/10/5/0,5/5
• (3) Der im Absatz (2) hergestellte Kleber wird auf den im Absatz (1) hergestellten Getriebeformkörper aufgebracht, der bei 25°C unter vermindertem Druck getrocknet und durch UV gehärtet und wärmegehärtet wird, um eine Klebeschicht zu bilden, die eine Harzmatrix enthält, welche eine quasi-homogene, verträgliche Struktur aufweist.
• (4) Dann wird die Oberfläche des Klebers durch Eintauchen in eine wässrige Lösung von Chromsäure (CrO₃, 500 g/l) bei 70°C für 15 Minuten aufgeraut, die in eine neutrale Lösung (hergestellt von Shipley) eingetaucht und mit Wasser gewaschen wird. Die aufgeraute Oberfläche hat Rmax = 10 μm gemäß JIS-B-0601.
• (5) Ein Palladiumkatalysator (hergestellt von Shipley) wird auf den mit der aufgerauten Oberfläche versehenen Träger aufgebracht, um die Oberfläche der Klebeschicht zu aktivieren, die einer Nickel-Phosphor-Plattierung in gewöhnlicher Weise unterworfen wird, um ein Getriebe mit einem metallischem Glanz herzustellen.

This example is an application embodiment of the invention to a plated, coated gear.

• (1) A gear molded body is usually manufactured using a polyimide.
• (2) An adhesive solution is obtained by mixing epoxy oligomer of cresol novolak type epoxy resin in which 25% of the epoxy groups are acrylated to give photosensitivity (CNA 25, molecular weight: 4000), PES (molecular weight: 17000), an imidazole type curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN) with caprolactone-modified trisisocyanurate (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M315) as a photosensitive monomer, benzophenone (BP) as Photo initiator and Michler's ketone as photosensitizer according to the following composition in DMDG, adding 30 parts by weight of rubber filler (manufactured by Japan Synthetic Rubber Co., Ltd.) with an average particle size of 5.0 μm, adjusting the viscosity to 1000 centipoise in a homodisper Shaking machine with NMP and subsequent kneading with three rollers. Resin composition: photosensitive epoxy / PES / M315 / BP / imidazole = 70/30/10/5 / 0.5 / 5
• (3) The adhesive produced in paragraph (2) is applied to the molded gear body manufactured in paragraph (1), which is dried at 25 ° C under reduced pressure and UV-cured and heat-cured to form an adhesive layer containing a resin matrix , which has a quasi-homogeneous, compatible structure.
• (4) Then, the surface of the adhesive is roughened by immersing in an aqueous solution of chromic acid (CrO ₃ , 500 g / l) at 70 ° C for 15 minutes, which is immersed in a neutral solution (manufactured by Shipley) and washed with water becomes. The roughened surface has Rmax = 10 μm according to JIS-B-0601.
• (5) A palladium catalyst (manufactured by Shipley) is applied to the roughened surface to activate the surface of the adhesive layer which is usually subjected to nickel-phosphorus plating to produce a gear with a metallic luster ,

The gearbox thus obtained is resistant to Chemicals such as acid and similar, and has excellent abrasion resistance due to the hard Surface, so no peeling the nickel layer from the surface occurs when using the gearbox.

Furthermore, there is no occurrence of cracking in the adhesive layer and no peeling of the plated nickel film by tension while using the gear caused.

If only the resin corresponds to the Resin matrix of the adhesive used in this example among the hardened above conditions will contain the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM in the same way as in Example 1.

If the resin mixture, which none rubber filler contains hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions an oscillation frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

Therefore, the matrix of this one Example used glue as a quasi-homogeneous, compatible structure viewed having.

(Example 26) A heat sink containing plate with semiconductor

• (1) Eine Kleberlösung wird erhalten durch Vermischen von Epoxyoligomer von Epoxyharz vom Kresol-Novolak-Typ, in welchem 25% der Epoxygruppen acryliert sind, um eine Fotoempfindlichkeit zu ergeben (CNA 25, Molekulargewicht: 4000), PES (Molekulargewicht: 17000), einem Härtungsmittel vom Imidazoltyp (hergestellt von Shikoku Kasei Co., Ltd., Handelsbezeichnung: 2E4MZ-CN) mit Caprolacton modifiziertem Trisisocyanurat (hergestellt von Toa Gosei Co., Ltd., Handelsbezeichnung: Aronics M315) als fotoempfindliches Monomer, Benzophenon (BP) als Fotoinitiator und Michlers Keton als Fotosensibilisierer gemäß der folgenden Zusammensetzung in DMDG, Versetzen mit 30 Gewichtsteilen Aluminiumnitridpulver mit einer mittleren Teilchengröße von 5,0 μm, Einstellen der Viskosität auf 1000 Centipoise in einer Homodisper-Schüttelmaschine mit NMP und anschließendes Verkneten durch drei Walzen. Harzzusammensetzung: fotoempfindlich gemachtes Epoxy/PES/M315/BP/ Imidazol = 70/30/10/5/0,5/5
• (2) Die Kleberlösung des Absatzes (1) wird auf einen Träger für eine Platte mit einem Halbleiter aufgebracht, die eine Aluminiumgrundlage und einen Leiterrahmen umfasst, welche bei 25°C unter vermindertem Druck getrocknet, durch UV gehärtet und wärmegehärtet wird, um eine Klebeschicht mit einer Harzmatrix, die eine quasi-homogene, verträgliche Struktur aufweist, zu bilden, in welcher die Aluminiumgrundlage mit der Klebeschicht überzogen ist und gleichzeitig die Aluminiumgrundlage einen integralen Bestandteil mit dem Leiterrahmen bildet.
• (3) Die Platte mit dem Halbleiter, die mit der Klebeschicht versehen ist, wird in Wasser eingetaucht, um Aluminiumnitridpulver von der Oberfläche der Klebeschicht aufzulösen und zu entfernen, um dadurch die Klebeschicht aufzurauen.
• (4) Ein Resistfilm für das Plattieren wird angefügt, welcher mit Licht belichtet und zur Bildung eines Plattierungsresists entwickelt wird. Dann wird er einer chemischen Kupferplattierung unterworfen, um einen Leiterkreis auf der Oberfläche zu bilden und auch eine elektrische Verbindung zu dem Leiterrahmen durch den Leiterkreis herzustellen.
• (5) Nachdem ein IC-Chip montiert ist, wird ein Gehäuse durch Verschließen mit einem Harz durch Vergießen gebildet, wodurch eine eine Wärmeableiteinrichtung enthaltende Platte mit einem Halbleiter hergestellt wird.

This example is an application embodiment of the invention to a semiconductor heater plate containing a heat sink.

• (1) An adhesive solution is obtained by mixing epoxy oligomer of cresol novolak type epoxy resin in which 25% of the epoxy groups are acrylated to give photosensitivity (CNA 25, molecular weight: 4000), PES (molecular weight: 17000), an imidazole type hardener (her provided by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN) with trisisocyanurate modified with caprolactone (manufactured by Toa Gosei Co., Ltd., trade name: Aronics M315) as a photosensitive monomer, benzophenone (BP) as a photo initiator and Michlers Ketone as Photosensitizer according to the following composition in DMDG, adding 30 parts by weight of aluminum nitride powder with an average particle size of 5.0 μm, adjusting the viscosity to 1000 centipoise in a homodisper shaker with NMP and then kneading by three rollers. Resin composition: photosensitive epoxy / PES / M315 / BP / imidazole = 70/30/10/5 / 0.5 / 5
• (2) The adhesive solution of paragraph (1) is applied to a support for a plate with a semiconductor, which comprises an aluminum base and a lead frame, which is dried at 25 ° C under reduced pressure, UV-cured and heat-cured to form an adhesive layer with a resin matrix, which has a quasi-homogeneous, compatible structure, in which the aluminum base is coated with the adhesive layer and at the same time the aluminum base forms an integral part with the lead frame.
• (3) The semiconductor plate provided with the adhesive layer is immersed in water to dissolve and remove aluminum nitride powder from the surface of the adhesive layer to thereby roughen the adhesive layer.
• (4) A resist film for plating is added, which is exposed to light and developed to form a plating resist. Then it is subjected to chemical copper plating to form a circuit on the surface and also to make an electrical connection to the lead frame through the circuit.
• (5) After an IC chip is mounted, a package is formed by sealing with a resin by molding, thereby producing a plate containing a heat sink with a semiconductor.

The heat dissipation device thus manufactured containing plate with a semiconductor has good heat dissipation, because the thermal conductivity of aluminum nitride is high.

Furthermore, the functional end group in the resin matrix in this example under high temperature conditions, high humidity and high pressure with formation of organic acids, such as Acetic acid, formic acid and the like, decomposes while Aluminum nitride is decomposed while under the above conditions ammonia to neutralize the acids is generated so that the corrosion of adhering metal is controlled can be.

If only the resin corresponds to the Resin matrix of the adhesive used in this example among the hardened above conditions will contain the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM in the same way as in Example 1.

If the resin mixture, which no Contains aluminum nitride powder, hardened peaks in the glass transition temperature Tg, measured by a viscoelastic test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

Therefore, the resin matrix of the in In this example, glue was used as a quasi-homogeneous, compatible structure viewed having.

(Example 27) Plated Shielding against electromagnetic interference (EMI)

This example is an embodiment of the invention for a clad shield against electromagnetic interference (EMI).

• (1) 65 parts by weight of cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-104S, epoxy equivalent: 220, molecular weight: 5000), 40 parts by weight of polyethersulfone (PES) (manufactured by ICI, trade name: Victrex, molecular weight: 17000), 5 parts by weight of hardening agent imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), 20 parts by weight of fine nickel powder with an average particle size of 5.5 μm and 10 parts by weight of the same powder with an average particle size of 0.5 μm mixed and with a solvent mixture of dimethylformamide / butyl cellosolve (1/1) added, meanwhile the viscosity set to 120 centipoise in a homodisper shaker, and then kneaded by three rollers to obtain an adhesive solution. In this case is the viscosity at room temperature 2 to 5 Pa · s.
• (2) The glue solution is produced on a filter paper using a roller coater ( by Thermatronics Boeki Co., Ltd.) applied, dried and by Heat to 80 ° C for 2 hours, to 120 ° C for 3 hours and to 150 ° C for 2 hours hardened, to form an adhesive layer with a thickness of about 20 microns.
• (3) The filter paper with the adhesive layers is in hydrochloric acid at 70 ° C for 15 minutes dipped to roughen the surface of the adhesive layer, and then dipped in a neutral solution (manufactured by Shipley) and washed with water. The roughened surface has Rmax = 10 μm according to JIS-B-0601.
• (4) A palladium catalyst (manufactured by Shipley) is manufactured on the carrier with the roughened surface of the Adhesive layer applied to activate the surface of the adhesive layer, and then subjected to nickel plating in the usual manner.

The plated shielding element thus obtained against electromagnetic interference (EMI) has an excellent shielding property because of the adhesive even contains nickel, and the plated film has a shielding effect and they have also a multi-layer structure.

There is no further crack in the adhesive layer caused even if the shield member is bent, so that the work of the shield member becomes easy.

If only the resin corresponds to the Resin matrix of the adhesive used in this example among the the above conditions is thermoset, contains the resulting hardened Product resin particles with an average particle size of not more than 0.1 μm, measured by TEM in the same way as in Example 1.

If the resin mixture, which is not a fine one Contains nickel powder, hardened peaks in the glass transition temperature Tg, measured by a visco elastic test under the conditions of a Vibration frequency of 6.28 rad / s and a rate of temperature rise of 5 ° C / min.

Therefore, it is believed that the resin matrix of the adhesive used in this example is a quasi-homogeneous, compatible Structure shows.

(Example 28) screw

• (1) A polycarbonate is formed into a helical support
• (2) 65 parts by weight of cresol novolak type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name: EOCN-104S, epoxy equivalent: 220, molecular weight: 5000), 40 parts by weight of polyethersulfone (PES) (manufactured by ICI, trade name: Victrex, molecular weight: 17000), 5 parts by weight of hardening agent imidazole type (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), 20 parts by weight of vinyl chloride resin powder with an average particle size of 5.5 μm and 10 parts by weight of the same powder with an average particle size of 0.5 μm mixed, stirred in a homodisper shaker and then kneaded by three rollers to obtain an adhesive solution.
• (3) The helical carrier of paragraph (1) is immersed in the above adhesive solution and then dried and by heating to 80 ° C for 2 hours, to 120 ° C for 5 hours and to 150 ° C for 2 hours hardened, to form an adhesive layer with a thickness of 20 μm. The hardened adhesive layer has a spherical one Domain structure, determined by SEM after the cracked surface with methylene chloride etched is.
• (4) Then the vinyl chloride resin powder on the surface of the Dissolved adhesive layer and removed by immersion in acetone to remove the surface of the Roughen the adhesive layer.
• (5) A palladium catalyst (manufactured by Shipley) is manufactured to the surface the adhesive layer is applied to activate the surface of the adhesive layer, which is then a chemical silver plating in the usual Way of making a screw is subjected.

The screw thus obtained contains silver in their surface, so that algae and the like due to the sterilizing effect of silver hardly adhere to it. Because the carrier a one piece body of polycarbonate, there is hardly any breakage by centrifugal force while Revolutions. conventional Screws are cut out of a metal block by cutting, so the cost increases. In contrast, the screw of this example as one piece moldings of the resin is formed so that the cost can be reduced.

In addition, no crack is due of tension during of the revolutions caused because the adhesive layer is tough.

INDUSTRIAL APPLICABILITY

As mentioned above, according to the invention, the resin composite of quasi-homogeneous compatible structure, co-continuous phase structure or spherical domain structure formed by a composition of the thermosetting resin or photosensitive resin with the thermoplastic resin is used as the heat-resistant resin matrix of an adhesive, thereby strengthening the resin matrix can to the adhesive property between the adhesive layer and the coated metal without lowering the To significantly improve heat resistance, electrical insulation properties and chemical stability.

Thus, various metal film can be coated Body, such as circuit boards with excellent peel strength and other industrial Parts are provided in a stable manner, even if the Wiring a higher Density and a higher Has pattern accuracy.

The invention is therefore not only on printed circuit boards, but also on different structural elements with adhering metal film and parts such as brake disc bodies, clutch hubs, Fuel injectors, fuel transport lines, Gears and the like in the field of automotive industry, lead frames, hermetic Degrees, ceramic packings, conductors, capacitors, resistors, solar electrodes, Hard drives and the like in the field of electrical and electronic industry, pumps, Valves, heat exchangers, Filters, screws, tools and bearings in the field of industrial Machines and building materials, such as decorative panels, etc., can be used and is beneficial in industry.

Claims (9)

A method of making an adhesive comprising the step of dispersing a decomposable, particulate Substance in an uncured, heat-resistant resin matrix, in which the heat-resistant resin matrix is a resin mixture consisting of a thermoplastic resin and at least one resin from a thermosetting Resin and a photosensitive resin, wherein the by decomposition removable, particulate Substance an emulsion polymerized amino resin with a low Degree of crosslinking is selected from a melamine resin, a urea resin and a guanamine resin, the particulate matter removable by decomposition by heating, Applying pressure or setting, the atmosphere decomposable is. A method of making an adhesive comprising the step of dispersing in an uncured, heat-resistant resin matrix a resin solution that with the matrix before curing immiscible and after hardening by dissolution is removable, wherein the heat-resistant resin matrix a resin mixture of a thermoplastic resin and at least a resin is selected made of a thermosetting resin and a photosensitive resin, and wherein the resin solution is a Silicone resin solution with epoxy group ends. Process for producing an adhesive by dispersing one by dissolution removable, granular Substance, selected from the group consisting of metal particles, in alkali-soluble Resin particles and soluble in an organic solvent Resin particles with the organic solvent selected from methyl ethyl ketone, benzene, toluene, dioxane, acetone, trichlorethylene, Ethylene dichloride, carbon disulfide, ethyl acetate, butyl acetate, Tetrahydrofuran, cyclohexanone, nitroethane, pyridine, chloroform and Carbon tetrachloride, in an uncured, heat-resistant resin matrix, wherein the heat resistant resin matrix is a resin mixture consisting of a thermoplastic resin and at least one resin selected from a thermosetting Resin and a photosensitive resin. A method according to any one of claims 1 to 3, wherein the photosensitive Resin is a derivative of a thermosetting Resin is where part of the functional groups in the thermosetting Resin is replaced by photosensitive groups. A method according to any one of claims 1 to 4, wherein the resin mixture a quasi-homogeneous, compatible structure, a co-continuous phase structure or a spherical domain structure forms. A method of making a laminate comprising an adhesive layer formed on a support and a roughened surface has the following steps: - Apply the by the Method obtainable from claim 1 Glue on the carrier to form a layer, - hardening the Layer and - roughen the surface the adhesive layer by decomposing those that can be removed by decomposition, particulate Substance under conditions of high humidity, high temperature and high Print. A method of making a laminate comprising an adhesive layer formed on a support and having a roughened surface, comprising the steps of: applying the adhesive obtainable by the method of claim 3 to the support to form a layer, curing the layer and - Roughening the surface of the adhesive layer by treatment with an alkali or an organic solvent. The method of claim 6 or 7, which further the step of applying a metal film to the roughened surface the adhesive layer comprises. Laminate comprising a support, one formed thereon Adhesive layer, the adhesive layer having a roughened surface, and a metal film arranged on the adhesive layer, the Laminate is obtainable by the method of claim 8.